C2-phenyl-substituted cyclic ketonols

ABSTRACT

The present invention relates to novel C 2 -phenyl-substituted cyclic ketoenols of the formula 
                         
in which W is methyl, X is alkyl, alkenyl or alkinyl, Y is hydrogen, methyl, ethyl, i-propyl, alkenyl or alkinyl, and Z is hydrogen, alkyl, alkenyl or alkinyl, with the proviso that at least one of X, Y, or Z represents a chain having at least two carbon atoms and with the further proviso that X is not ethyl when Z is hydrogen and Y is methyl, and CKE represents the group
 
                         
in which B is hydrogen, alkyl or alkoxyalkyl, A and Q 1  together are optionally substituted alkanediyl or alkenediyl, Q 2  is represents hydrogen or C 1 -C 4 -alkyl, and G represents hydrogen or an acyl or acyl-like group, to a plurality of processes for their preparation and to their use as pesticides and herbicides.

This application is a Divisional Application of U.S. application Ser No.13/029,497, filed Feb. 17, 2011, which is a Divisional of U.S. Ser. No.10/239,331, filed Dec. 16, 2002, now U.S. Pat. No. 7,915,282, which is aNational Stage Application of PCT/EP01/03215, filed Mar. 21, 2001, whichclaim priority to German Application 100 16 544.3, filed Apr. 3, 2000,each hereby incorporated by reference in their entireties.

The present invention relates to novel C₂-phenyl-substituted cyclicketoenols, to a plurality of processes for their preparation and totheir use as pesticides and herbicides.

Pharmacological properties of 3-acyl-pyrrolidine-2,4-diones have alreadybeen described (S. Suzuki et al. Chem. Pharm. Bull. 15 1120 (1967)).Furthermore, N-phenylpyrrolidine-2,4-diones have been synthesized by R.Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985, 1095). Abiological activity of these compounds has not been described.

EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a similarstructure (3-aryl-pyrrolidine-2,4-diones) of which, however, noherbicidal, insecticidal or acaricidal activity has become known.Unsubstituted bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP-A-355 599 and EP-A-415 211) and substituted monocyclic3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077)having herbicidal, insecticidal or acaricidal activity are known.

Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives(EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063,EP-A-521 334, EP-A-596 298. EP-A-613 884, EP-A-613 885, WO 94/01 997, WO95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO97/01 535, WO 97/02 243, WO 97/36 868. WO 97/43275, WO 98/05638, WO98/06721, WO 98/25928, WO 99/16748, WO 99/24437. WO 99/43649. WO99/48869 and WO 99/55673).

It is known that certain substituted Δ³-dihydrofuran-2-one derivativeshave herbicidal properties (cf. DE-A-4 014 420). The synthesis of thetetronic acid derivatives used as starting materials (such as, forexample,3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-Δ³-dihydrofuran-2-one)is likewise described in DE-A-4 014420.

Compounds of a similar structure are known from the publication Campbellet al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76, without anyinsecticidal and/or acaricidal activity being mentioned. Furthermore,3-aryl-Δ³-dihydrofuranone derivatives having herbicidal, acaricidal andinsecticidal properties are known from EP-A-528 156, EP-A-0 647 637, WO95/26 345, WO 96/20 196, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO97/02 243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO99/43649, WO 99/48869 and WO 99/55673. 3-Aryl-Δ³-dihydrothiphenonederivatives are likewise known (WO 95/26 345, 96/25 395, WO 97/01 535,WO 97/02 243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO99/43649, WO 99/48869, WO 99/55673).

Certain phenyl-pyrone derivatives which are unsubstituted in the phenylring have already become known (cf. A. M. Chirazi, T. Kappe and E.Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K.Heidenbluth, Chem. Ber. 91, 2849), a possible use of these compounds aspesticides not being mentioned. Phenyl-pyrone derivatives which aresubstituted in the phenyl ring and have herbicidal, acaricidal andinsecticidal properties are described in EP-A-588 137, WO 96/25 395, WO96/35 664, WO 97/01 535, WO 97/02 243, WO 97/16 436, WO 97/19 941, WO97/36 868, WO 98/05638, WO 99/43649, WO 99/48869 and WO 99/55673.

Certain 5-phenyl-1,3-thiazine derivatives which are unsubstituted in thephenyl ring have already become known (cf. E. Ziegler and E. Steiner,Monatsh. 95, 147 (1964), R. Ketcham, T. Kappe and E. Ziegler, J.Heterocycl. Chem. 10, 223 (1973)), a possible use of these compounds aspesticides not being mentioned. 5-Phenyl-1,3-thiazine derivatives whichare substituted in the phenyl ring and have herbicidal, acaricidal andinsecticidal activity are described in WO 94/14 785, WO 96/02 539, WO96/35 664, WO 97/01 535, WO 97/02 243, WO 97/02 243, WO 97/36 868, WO99/05638, WO 99/43649, WO 99/48869 and WO 99/55673.

It is known that certain substituted 2-arylcyclopentanediones haveherbicidal and acaricidal properties (cf., for example, U.S. Pat. Nos.4,283,348; 4,338,122; 4,436,666; 4,526,723; 4,551,547; 4,632,698; WO96/01 798; WO 96/03 366, WO 97/14 667 and also WO 98/39281, WO 99/43649,WO 99/48869, WO 99/55673). Moreover, compounds of a similar structureare known; 3-hydroxy-5,5-dimethyl-2-phenylcyclo-pent-2-en-1-one from thepublication Micklefield et al., Tetrahedron, (1992), 7519-26 and thenatural product involutine(−)-cis-5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxyphenyl)-cyclopent-2-en-onefrom the publication Edwards et al., J. Chem. Soc. S, (1967), 405-9. Aninsecticidal or acaricidal activity is not described. Moreover,2-(2,4,6-trimethylphenyl)-1,3-indanedione is known from the publicationJ. Economic Entomology, 66, (1973), 584 and the Offenlegungsschrift DE-A2 361 084, with herbicidal and acaricidal activities being mentioned.

It is known that certain substituted 2-arylcyclohexanediones haveherbicidal and acaricidal properties (U.S. Pat. Nos. 4,175,135,4,209,432, 4,256,657, 4,256,658, 4,256,659, 4,257,858, 4,283,348,4,303,669, 4,351,666, 4,409,153, 4,436,666, 4,526,723, 4,613,617,4,659,372, DE-A 2 813 341, and also Wheeler, T. N., J. Org. Chem. 44,4906 (1979)), WO 99/43649, WO 99/48869, WO 99/55673).

However, the activity and the activity spectrum of these compounds are,in particular at low application rates and concentrations, not alwaysentirely satisfactory. Furthermore, the compatibility of these compoundswith plants is not always sufficient.

This invention, accordingly, provides novel compounds of the formula (I)

in which

W represents hydrogen, alkyl, alkenyl or alkinyl,

X represents alkyl, alkenyl or alkinyl,

Y represents hydrogen, methyl, ethyl, i-propyl, alkenyl or alkinyl,

Z represents hydrogen, alkyl, alkenyl or alkinyl,

with the proviso that at least one of the radicals W, X, Y or Zrepresents a chain having at least two carbon atoms,

CKE represents one of the groups

-   -   in which        -   A represents hydrogen, represents in each case optionally            halogen-substituted alkyl, alkenyl, alkoxyalkyl,            alkylthioalkyl, represents saturated or unsaturated,            optionally substituted cycloalkyl in which optionally at            least one ring atom is replaced by a heteroatom, or            represents in each case optionally halogen-, alkyl-,            halogenoalkyl-, alkoxy-, halogenoalkoxy-, cyano- or            nitro-substituted aryl, arylalkyl or hetaryl,        -   B represents hydrogen, alkyl or alkoxyalkyl, or        -   A and B together with the carbon atom to which they are            attached represent a saturated or unsaturated unsubstituted            or substituted cycle which optionally contains at least one            heteroatom,        -   D represents hydrogen or represents an optionally            substituted radical from the group consisting of alkyl,            alkenyl, alkinyl, alkoxyalkyl, saturated or unsaturated            cycloalkyl in which optionally one or more ring members are            replaced by heteroatoms, arylalkyl, aryl, hetarylalkyl and            hetaryl or        -   A and D together with the atoms to which they are attached            represent a saturated or unsaturated cycle which is            unsubstituted or substituted in the A,D moiety and which            optionally contains at least one heteroatom, or        -   A and Q¹ together represent alkanediyl or alkenediyl, each            of which is optionally substituted by hydroxyl or by in each            case optionally substituted alkyl, alkoxy, alkylthio,            cycloalkyl, benzyloxy or aryl or        -   Q¹ represents hydrogen or alkyl,        -   Q², Q⁴, Q⁵ and Q⁶ independently of one another each            represent hydrogen or alkyl,        -   Q³ represents hydrogen, alkyl, alkoxyalkyl, alkylthioalkyl,            optionally substituted cycloalkyl (in which optionally one            methylene group is replaced by oxygen or sulphur) or            optionally substituted phenyl, or        -   Q³ and Q⁴ together with the carbon atom to which they are            attached represent a saturated or unsaturated unsubstituted            or substituted cycle which optionally contains a heteroatom,        -   G represents hydrogen (a) or represents one of the groups

-   -   -   -   in which            -   E represents a metal ion equivalent or an ammonium ion,            -   L represents oxygen or sulphur,            -   M represents oxygen or sulphur,            -   R¹ represents in each case optionally                halogen-substituted alkyl, alkenyl, alkoxyalkyl,                alkylthioalkyl, polyalkoxyalkyl or optionally halogen-,                alkyl- or alkoxy-substituted cycloalkyl which may be                interrupted by at least one heteroatom, in each case                optionally substituted phenyl, phenylalkyl, hetaryl,                phenoxyalkyl or hetaryloxyalkyl,            -   R² represents in each case optionally                halogen-substituted alkyl, alkenyl, alkoxyalkyl,                polyalkoxyalkyl or represents in each case optionally                substituted cycloalkyl, phenyl or benzyl,            -   R³, R⁴ and R⁵ independently of one another each                represent in each case optionally halogen-substituted                alkyl, alkoxy, alkylamino, dialkylamino, alkylthio,                alkenylthio, cycloalkylthio and represent in each case                optionally substituted phenyl, benzyl, phenoxy or                phenylthio,            -   R⁶ and R⁷ independently of one another each represent                hydrogen, in each case optionally halogen-substituted                alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl,                represent optionally substituted phenyl, represent                optionally substituted benzyl, or together with the N                atom to which they are attached represent a cycle which                is optionally interrupted by oxygen or sulphur.

Depending, inter alia, on the nature of the substituents, the compoundsof the formula (I) can be present as geometrical and/or optical isomersor mixtures of isomers in varying compositions, which can be separated,if desired, in a customary manner. The present invention provides boththe pure isomers and the isomer mixtures, their preparation and use andalso compositions comprising them. In the following, for simplicity,however, the compounds of the formula (I) are always referred to,although both pure compounds and, if appropriate, mixtures havingdifferent proportions of isomeric compounds are intended.

Including the meanings (1) to (7) of the group CKE, the followingprincipal structures (I-1) to (I-7) result:

in which

A, B, D, G, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as definedabove.

Including the various meanings of (a), (b), (c), (d), (e), (f) and (g)of the group G, the following principal structures (I-1-a) to (I-1-g)result if CKE represents the group (1):

in which

A, B, D, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-2-a) to (I-2-g)result if CKE represents the group (2):

in which

A, B, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-3-a) to (I-3-g)result if CKE represents the group (3): (I-3-a): (I-3-b):

in which

A, B, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Depending on the position of the substituent G, the compounds of theformula (I-4) can be present in two isomeric forms of the formulae(I-5-A) and (I-5-B)

which is meant to be indicated by the dashed line in the formula (I-4).

The compounds of the formulae (I-4-A) and (I-4-B) can be present both asmixtures and in the form of their pure isomers. Mixtures of thecompounds of the formulae (I-4-A) and (I-4-B) can be separated, ifdesired, in a known manner by physical methods, for example bychromatographic methods.

For reasons of clarity, hereinbelow in each case only one of thepossible isomers is given. This does not exclude that the compounds may,if appropriate, be present in the form of the isomer mixtures or in therespective other isomeric form.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-4-a) to (I-4-g)result if CKE represents the group (4): (I-4-a): (I-4-b):

in which

A, D, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-5-a) to (I-5-g)result if CKE represents the group (5): (I-5-a): (I-5-b):

in which

A, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Depending on the position of the substituent G, the compounds of theformula (I-6) can be present in the two isomeric forms of the formula(I-6-A) and (I-6-B)

which is meant to be indicated by the dashed line in the formula (I).

The compounds of the formulae (I-6-A) and (I-6-B) can be present both asmixtures and in the form of their pure isomers. Mixtures of thecompounds of the formulae (I-6-A) and (I-6-B) can be separated, ifdesired, by physical methods, for example by chromatographic methods.

For reasons of clarity, hereinbelow in each case only one of thepossible isomers is given. This does not exclude that the compounds may,if appropriate, be present in the form of the isomer mixtures or in therespective other isomeric form.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-6-a) to (I-6-g)result:

in which

A, B, Q¹, Q², E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ areeach as defined above.

Depending on the position of the substituent G, the compounds of theformula (I-7) can be present in two isomeric forms of the formulae(I-7-A) and (I-7-B) which is meant to be indicated by the dashed line inthe formula (I-7):

The compounds of the formulae (I-7-A) and (I-7-B) can be present both asmixtures and in the form of their pure isomers. Mixtures of thecompounds of the formulae (I-7-A) and (I-7-B) can be separated, ifdesired, by physical methods, for example by chromatographic methods.

For reasons of clarity, hereinbelow in each case only one of thepossible isomers is given. This does not exclude that the compound may,if appropriate, be present in the form of the isomer mixture or in therespective other isomeric form.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-7-a) to (I-7-g)result:

in which

A, B, E, L, M, Q³, Q⁴, Q⁵, Q⁶, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷are each as defined above.

Furthermore, it has been found that the novel compounds of the formula(I) are obtained by one of the processes described below:

-   (A) Substituted 3-phenylpyrrolidine-2,4-diones or their enols of the    formula (I-1-a)

-   -   in which    -   A, B, D, W, X, Y and Z are each as defined above    -   are obtained when    -   N-acylamino acid esters of the formula (II)

-   -   in which    -   A, B, D, W, X, Y and Z are each as defined above    -   and    -   R⁸ represents alkyl (preferably C₁-C₆-alkyl),    -   are condensed intramolecularly in the presence of a diluent and        in the presence of a base.

-   (B) Moreover, it has been found that substituted    3-phenyl-4-hydroxy-Δ³-di-hydrofuranone derivatives of the formula    (I-2-a)

-   -   in which    -   A, B, W, X, Y and Z are each as defined above are obtained when    -   carboxylic esters of the formula (III)

-   -   in which    -   A, B, W, X, Y, Z and R⁸ are each as defined above are condensed        intramolecularly in the presence of a diluent and in the        presence of a base.

-   (C) Furthermore, it has been found that substituted    3-phenyl-4-hydroxy-Δ³-di-hydrothiophenone derivatives of the formula    (I-3-a)

-   -   in which    -   A, B, W, X, Y and Z are each as defined above    -   are obtained when    -   β-ketocarboxylic esters of the formula (IV)

-   -   in which    -   A, B, W, X, Y, Z and R⁸ are each as defined above and    -   V represents hydrogen, halogen, alkyl (preferably C₁-C₆-alkyl)        or alkoxy (preferably C₁-C₈-alkoxy)    -   are cyclized intramolecularly, if appropriate in the presence of        a diluent and in the presence of an acid.

-   (D) Furthermore, it has been found that the novel substituted    3-phenylpyrone derivatives of the formula (I-4-a)

-   -   in which    -   A, D, W, X, Y and Z are each as defined above    -   are obtained when    -   carbonyl compounds of the formula (V)

-   -   in which    -   A and D are each as defined above or their silyl enol ethers of        the formula (Va)

-   -   in which    -   A, D and R⁸ are each as defined above    -   are reacted with ketene acid halides of the formula (VI)

-   -   in which    -   W, X, Y and Z are each as defined above and    -   Hal represents halogen (preferably chlorine or bromine),    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid acceptor.

Furthermore, it has been found

-   (E) that the novel substituted phenyl-1,3-thiazine derivatives of    the formula (I-5-a)

-   -   in which    -   A, W, X, Y and Z are each as defined above are obtained when    -   thioamides of the formula (VII)

-   -   in which    -   A is as defined above are reacted with ketene acid halides of        the formula (VI)

-   -   in which    -   Hal, W, X, Y and Z are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid acceptor.

Furthermore, it has been found

-   (F) that compounds of the formula (I-6-a)

-   -   in which    -   A, B, Q¹, Q², W, X, Y and Z are each as defined above    -   are obtained when    -   ketocarboxylic esters of the formula (VIII)

-   -   in which    -   A, B, Q¹, Q², W, X, Y and Z are each as defined above and    -   R⁸ represents alkyl (in particular C₁-C₈-alkyl)        -   are cyclized intramolecularly, if appropriate in the            presence of a diluent and in the presence of a base.

Moreover, it has been found

-   (G) that compounds of the formula (I-7-a)

-   -   in which    -   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as defined above    -   are obtained when    -   6-aryl-5-keto-hexanoic esters of the formula (IX)

-   -   in which    -   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as defined above        and    -   R⁸ represents alkyl (preferably C₁-C₆-alkyl)    -   are condensed intramolecularly in the presence of a diluent and        in the presence of a base;

-   (H) that compounds of the formulae (I-1(a-g)) to (I-7(a-g)) shown    above in which A, B, D, G, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are    each as defined above,    -   where one, at most two, radicals W, X, Y or Z represent R²²—C═C—        or

R²² represents hydrogen or C₁-C₄-alkyl, preferably hydrogen orC₁-C₂-alkyl and particularly preferably hydrogen,are obtained when compounds of the formulae (I-1′(a-g)) to (I-7′(a-g)),

-   -   in which    -   A, B, D, G, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W′, X′, Y′ and Z′ are each        as defined above and where the apostrophe ' means that one, at        most two, radicals W, X, Y and Z in this process represent        chlorine, bromine, iodine, preferably bromine, with the proviso        that the other radicals W, X, Y or Z do not represent alkenyl or        alkinyl    -   are reacted with silylacetylenes of the formula (X-a) or        vinylstannanes of the formula (X-b)

-   -   in which alk preferably represents C₁-C₄-alkyl and    -   R²¹ preferably represents C₁-C₄-alkyl or phenyl,    -   R²² preferably represents hydrogen or C₁-C₄-alkyl, particularly        preferably hydrogen or C₁-C₂-alkyl and very particularly        preferably hydrogen,    -   in the presence of a solvent, if appropriate in the presence of        a base and a catalyst, particularly suitable catalysts being        palladium complexes.

Moreover, it has been found

-   (I) that the compounds of the formulae (I-1-b) to (I-7-b) shown    above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R¹, W, X, Y and Z    are each as defined above are obtained when compounds of the    formulae (I-1-a) to (I-7-a) shown above in which A, B, D, Q¹, Q²,    Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as defined above are in each    case-   (α) reacted with acid halides of the formula (XI)

-   -   in which    -   R¹ is as defined above and    -   Hal represents halogen (in particular chlorine or bromine)    -   or

-   (β) reacted with carboxylic anhydrides of the formula (XII)    R¹—CO—O—CO—R¹  (XII)    -   in which    -   R¹ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;

-   (J) that the compounds of the formulae (I-1-c) to (I-7-c) shown    above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R², M, W, X, Y and Z    are each as defined above and L represents oxygen are obtained when    compounds of the formulae (I-1-a) to (I-7-a) shown above in which A,    B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as defined    above are in each case    -   reacted with chloroformic esters or chloroformic thioesters of        the formula (XIII)        R²-M-CO—Cl  (XIII)    -   in which    -   R² and M are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;

-   (K) that compounds of the formulae (I-1-c) to (I-7-c) shown above in    which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R², M, W, X, Y and Z are in    each case as defined above and L represents sulphur are obtained    when compounds of the formulae (I-1-a) to (I-7-a) shown above in    which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are in each    case as defined above are in each case reacted with    chloromonothioformic esters or chlorodithioformic esters of the    formula (XIV)

-   -   in which    -   M and R² are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder    -   and

-   (L) that compounds of the formulae (I-1-d) to (I-7-d) shown above in    which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R³, W, X, Y and Z are each as    defined above are obtained when compounds of the formulae (I-Ia) to    (I-7-a) shown above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X,    Y and Z are each as defined above are in each case    -   reacted with sulphonyl chlorides of the formula (XV)        R³—SO₂—Cl  (XV)    -   in which    -   R³ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder,

-   (M) that compounds of the formulae (I-1-e) to (I-7-e) shown above in    which A, B, D, L, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R⁴, R⁵, W, X, Y and Z are    each as defined above are obtained when compounds of the formulae    (I-1-a) to (I-7-a) shown above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵,    Q⁶, W, X, Y and Z are each as defined above are in each case reacted    with phosphorus compounds of the formula (XVI)

-   -   in which    -   L, R⁴ and R⁵ are each as defined above and    -   Hal represents halogen (in particular chlorine or bromine),    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder,

-   (N) that compounds of the formulae (I-1-f) to (I-7-f) shown above in    which A, B, D, E, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as    defined above are obtained when compounds of the formulae (I-1-a) to    (I-7-a) shown above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X,    Y and Z are each as defined above are in each case    -   reacted with metal compounds or amines of the formulae (XVII) or        (XVIII)        Me(OR¹⁰)_(t)  (XVII)

-   -   in which    -   Me represents a mono- or divalent metal (preferably an alkali        metal or alkaline earth metal, such as lithium, sodium,        potassium, magnesium or calcium),    -   t represents the number 1 or 2,    -   R¹⁰, R¹¹, R¹² independently of one another each represents        hydrogen or alkyl (preferably C₁-C₈-alkyl),    -   if appropriate in the presence of a diluent,

-   (O) that compounds of the formulae (I-1-g) to (I-7-g) shown above in    which A, B, D, L, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R⁶, R⁷, W, X, Y and Z are    each as defined above are obtained when compounds of the formulae    (I-1-a) to (I-7-a) shown above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵,    Q⁶, W, X, Y and Z are each as defined above are in each case

-   (α) reacted with isocyanates or isothiocyanates of the formula (XIX)    R⁶—N═C=L  (XIX)    -   in which    -   R⁶ and L are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a catalyst, or

-   (β) reacted with carbamoyl chlorides or thiocarbamoyl chlorides of    the formula (XX)

-   -   in which    -   L, R⁶ and R⁷ are each as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder.

Furthermore, it has been found that the novel compounds of the formula(I) have very good activity as pesticides, preferably as insecticides,acaricides and herbicides.

The formula (I) provides a general definition of the compounds accordingto the invention. Preferred substituents or ranges of the radicalslisted in the formulae mentioned hereinabove and hereinbelow areillustrated below.

-   W preferably represents hydrogen, C t-C₆-alkyl, C₂-C₆-alkenyl or    ethinyl.-   X preferably represents C₁-C₆-alkyl, C₂-C₆-alkenyl or ethinyl.-   Y preferably represents hydrogen, methyl, ethyl, i-propyl,    C₂-C₆-alkenyl or ethinyl.-   Z preferably represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl or    ethinyl    with the proviso that at least one of the radicals W, X, Y and Z    represents a chain having at least two carbon atoms.

CKE preferably represents one of the groups

-   A preferably represents hydrogen or in each case optionally    halogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl,    C₁-C₁₀-alkoxy-C₁-C₈-alkyl, C₁-C₁₀-alkylthio-C₁-C₆-alkyl, optionally    halogen-, C₁-C₆-alkyl- or C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl    in which optionally one or two not directly adjacent ring members    are replaced by oxygen and/or sulphur or represents in each case    optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-halogenoalkyl-,    C₁-C₆-alkoxy-, C₁-C₆-halogenoalkoxy-, cyano- or nitro-substituted    phenyl or naphthyl, hetaryl having 5 to 6 ring atoms (for example    furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, pyrimidyl,    thiazolyl or thienyl), phenyl-C₁-C₆-alkyl or naphthyl-C₁-C₆-alkyl.-   B preferably represents hydrogen, C₁-C₁₂-alkyl or    C₁-C₈-alkoxy-C₁-C₆-alkyl, or-   A, B and the carbon atom to which they are attached preferably    represent saturated C₃-C₁₀-cycloalkyl or unsaturated    C₅-C₁₀-cycloalkyl in which optionally one ring member is replaced by    oxygen or sulphur and which are optionally mono- or disubstituted by    C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl, C₁-C₈-halogenoalkyl, C₁-C₈-alkoxy,    C₁-C₈-alkylthio, halogen or phenyl, or-   A, B and the carbon atom to which they are attached preferably    represent C₃-C₆-cycloalkyl which is substituted by an alkylenediyl    group which optionally contains one or two not directly adjacent    oxygen and/or sulphur atoms and which is optionally    C₁-C₄-alkyl-substituted, or by an alkylenedioxyl group or by    alkenedithioyl group which, together with the carbon atom to which    it is attached, forms a further five- to eight-membered ring, or-   A, B and the carbon atom to which they are attached preferably    represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which two    substituents together with the carbon atoms to which they are    attached represent in each case optionally C₁-C₆-alkyl-,    C₁-C₆-alkoxy- or halogen-substituted C₂-C₆-alkanediyl,    C₂-C₆-alkenediyl or C₄-C₆-alkanedienediyl in which optionally one    methylene group is replaced by oxygen or sulphur.-   D preferably represents hydrogen, in each case optionally    halogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkinyl,    C₁-C₁₀-alkoxy-C₂-C₈-alkyl optionally halogen-, C₁-C₄-alkyl-,    C₁-C₄-alkoxy- or C₁-C₄-halogenoalkyl-substituted C₃-C₈-cycloalkyl in    which optionally one ring member is replaced by oxygen or sulphur or    in each case optionally halogen-, C₁-C₆-alkyl-,    C₁-C₆-halogenoalkyl-, C₁-C₆-alkoxy-, C₁-C₆-halogenoalkoxy-, cyano-    or nitro-substituted phenyl, hetaryl having 5 or 6 ring atoms (for    example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl,    pyrimidyl, pyrrolyl, thienyl or triazoyl), phenyl-C₁-C₆-alkyl or    hetaryl-C₁-C₆-alkyl having 5 or 6 ring atoms (for example furanyl,    imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl,    thienyl or triazoyl), or-   A and D together represent in each case optionally substituted    C₃-C₆-alkanediyl or C₃-C₆-alkenediyl in which optionally one    methylene group is replaced by a carbonyl group, oxygen or sulphur,    possible substituents being in each case: halogen, hydroxyl,    mercapto or in each case optionally halogen-substituted    C₁-C₁₀-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₇-cycloalkyl,    phenyl or benzyloxy, or a further C₃-C₆-alkanediyl grouping,    C₃-C₆-alkenediyl grouping or a butadienyl grouping which is    optionally substituted by C₁-C₆-alkyl or in which optionally two    adjacent substituents together with the carbon atoms to which they    are attached form a further saturated or unsaturated cycle having 5    or 6 ring atoms (in the case of the compound of the formula (I-1), A    and D, together with the atoms to which they are attached, then    represent, for example, the groups AD-1 to AD-10 mentioned further    below) which cycle may contain oxygen or sulphur, or which may    optionally contain one of the groups below

-   -   or

-   A and Q¹ preferably together represent C₃-C₆-alkanediyl or    C₄-C₆-alkenediyl, each of which is optionally mono- or disubstituted    by identical or different substituents selected from the group    consisting of halogen, hydroxyl, C₁-C₁₀-alkyl, C₁-C₆-alkoxy,    C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, each of which is optionally mono-    to trisubstituted by identical or different halogens, and benzyloxy    and phenyl, each of which is optionally mono- to trisubstituted by    identical or different substituents selected from the group    consisting of halogen, C₁-C₆-alkyl and C₁-C₆-alkoxy, and which    furthermore optionally contains one of the groups below

-   -   or is bridged by a C₁-C₂-alkanediyl group or by an oxygen atom,        or

-   Q¹ preferably represents hydrogen or C₁-C₄-alkyl.

-   Q², Q⁴, Q⁵ and Q⁶ independently of one another each preferably    represent hydrogen or C₁-C₄-alkyl.

-   Q³ preferably represents hydrogen, C₁-C₆-alkyl,    C₁-C₆-alkoxy-C₁-C₂-alkyl, C₁-C₆-alkylthio-C₁-C₂-alkyl, optionally    C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted C₃-C₈-cycloalkyl in which    optionally one methylene group is replaced by oxygen or sulphur or    optionally halogen-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,    C₁-C₂-halogenoalkyl-, C₁-C₂-halogenoalkoxy-, cyano- or    nitro-substituted phenyl, or

-   Q³ and Q⁴ together with the carbon atom to which they are attached    preferably represent an optionally C₁-C₄-alkyl-, C₁-C₄-alkoxy- or    C₁-C₂-halogenoalkyl-substituted C₃-C₇-ring in which optionally one    ring member is replaced by oxygen or sulphur.

-   G preferably represents hydrogen (a) or represents one of the groups

in particular (a), (b), (c) or (g)

-   -   in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.

-   R¹ particularly preferably represents in each case optionally    halogen-substituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,    C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl,    poly-C₁-C₈-alkoxy-C₁-C₈-alkyl or optionally halogen-, C₁-C₆-alkyl or    C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl in which optionally one or    more (preferably not more than two) not directly adjacent ring    members are replaced by oxygen and/or sulphur,    -   represents optionally halogen-, cyano-, nitro-, C₁-C₆-alkyl-,        C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl-, C₁-C₆-halogenoalkoxy-,        C₁-C₆-alkylthio- or C₁-C₆-alkylsulphonyl-substituted phenyl,    -   represents optionally halogen-, nitro-, cyano-, C₁-C₆-alkyl-,        C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl- or        C₁-C₆-halogenoalkoxy-substituted phenyl-C₁-C₆-alkyl,    -   represents optionally halogen- or C₁-C₆-alkyl-substituted 5- or        6-membered hetaryl (for example pyrazolyl, thiazolyl, pyridyl,        pyrimidyl, furanyl or thienyl),    -   represents optionally halogen- or C₁-C₆-alkyl-substituted        phenoxy-C₁-C₆-alkyl or    -   represents optionally halogen-, amino- or        C₁-C₆-alkyl-substituted 5- or 6-membered hetaryloxy-C₁-C₆-alkyl        (for example pyridyloxy-C₁-C₆-alkyl, pyrimidyloxy-C₁-C₆-alkyl or        thiazolyloxy-C₁-C₆-alkyl). R² preferably represents in each case        optionally halogen-substituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,        C₁-C₈-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂-C₈-alkyl,    -   represents optionally halogen-, C₁-C₆-alkyl- or        C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl or    -   represents in each case optionally halogen-, cyano-, nitro-,        C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl- or        C₁-C₆-halogenoalkoxy-substituted phenyl or benzyl.

-   R³ preferably represents optionally halogen-substituted C₁-C₈-alkyl    or represents in each case optionally halogen-, C₁-C₆-alkyl-,    C₁-C₆-alkoxy-, C₁-C₄-halogenoalkyl-, C₁-C₄-halogenoalkoxy-, cyano-    or nitro-substituted phenyl or benzyl.

-   R⁴ and R⁵ independently of one another each preferably represent in    each case optionally halogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy,    C₁-C₈-alkyl-amino, di-(C₁-C₈-alkyl)amino, C₁-C₈-alkylthio,    C₂-C₈-alkenylthio, C₃-C₇-cycloalkylthio or represent in each case    optionally halogen-, nitro-, cyano-, C₁-C₄-alkoxy-,    C₁-C₄-halogenoalkoxy-, C₁-C₄-alkylthio-, C₁-C₄-halogenoalkylthio-,    C₁-C₄-alkyl- or C₁-C₄-halogenoalkyl-substituted phenyl, phenoxy or    phenylthio.

-   R⁶ and R⁷ independently of one another each preferably represent    hydrogen, represent in each case optionally halogen-substituted    C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl,    C₁-C₈-alkoxy-C₁-C₈-alkyl, represent optionally halogen-,    C₁-C₈-halogenoalkyl-, C₁-C₈-alkyl- or C₁-C₈-alkoxy-substituted    phenyl, optionally halogen-, C₁-C₈-alkyl-, C₁-C₈-halogenoalkyl- or    C₁-C₈-alkoxy-substituted benzyl or together represent an optionally    C₁-C₄-alkyl-substituted C₃-C₆-alkylene radical in which optionally    one carbon atom is replaced by oxygen or sulphur.

-   R¹³ preferably represents hydrogen, represents in each case    optionally halogen-substituted C₁-C₈-alkyl or C₁-C₈-alkoxy,    represents optionally halogen-, C₁-C₄-alkyl- or    C₁-C₄-alkoxy-substituted C₃-C₈-cycloalkyl in which optionally one    methylene group is replaced by oxygen or sulphur, or represents in    each case optionally halogen-, C₁-C₆-alkyl C₁-C₆-alkoxy-,    C₁-C₄-halogenoalkyl-, C₁-C₄-halogenoalkoxy-, nitro- or    cyano-substituted phenyl, phenyl-C₁-C₄-alkyl or phenyl-C₁-C₄-alkoxy.

-   R¹⁴ preferably represents hydrogen or C₁-C₈-alkyl, or

-   R¹³ and R¹⁴ together preferably represent C₄-C₆-alkanediyl.

-   R¹⁵ and R¹⁶ are identical or different and each preferably    represents C₁-C₆-alkyl, or

-   R¹⁵ and R¹⁶ together preferably represent a C₂-C₄-alkanediyl radical    which is optionally substituted by C₁-C₆-alkyl, C₁-C₆-halogenoalkyl    or by optionally halogen-, C₁-C₆-alkyl-, C₁-C₄-halogenoalkyl-,    C₁-C₆-alkoxy-, C₁-C₄-halogenoalkoxy-, nitro- or cyano-substituted    phenyl.

-   R¹⁷ and R¹⁸ independently of one another each preferably represent    hydrogen, represent optionally halogen-substituted C₁-C₈-alkyl or    represent optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,    C₁-C₄-halogenoalkyl-, C₁-C₄-halogenoalkoxy-, nitro- or    cyano-substituted phenyl, or

-   R¹⁷ and R¹⁸ together with the carbon atom to which they are attached    preferably represent a carbonyl group or represent optionally    halogen-, C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted C₅-C₇-cycloalkyl    in which optionally one methylene group is replaced by oxygen or    sulphur.

-   R¹⁹ and R²⁰ independently of one another each particularly    preferably represent C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy,    C₁-C₁₀-alkylamino, C₃-C₁₀-alkenylamino, di-(C₁-C₁₀-alkyl)amino or    di-(C₃-C₁₀-alkenyl)amino.

-   W particularly preferably represents hydrogen, C₁-C₄-alkyl,    C₂-C₄-alkenyl or ethinyl.

-   X particularly preferably represents C₁-C₄-alkyl, C₂-C₄-alkenyl or    ethinyl.

-   Y particularly preferably represents hydrogen, methyl, ethyl,    i-propyl, C₂-C₄-alkenyl or ethinyl.

-   Z particularly preferably represents hydrogen, C₁-C₄-alkyl,    C₂-C₄-alkenyl or ethinyl    with the proviso that at least one of the radicals W, X, Y or Z    represents a chain having at least two carbon atoms, where at most    only one of the radicals W, X, Y or Z may represent C₂-C₄-alkenyl or    ethinyl.

CKE particularly preferably represents one of the groups

-   A particularly preferably represents in each case optionally    fluorine- or chlonne-substituted C₁-C₆-alkyl,    C₁-C₄-alkoxy-C₁-C₂-alkyl, optionally C₁-C₂-alkyl- or    C₁-C₂-alkoxy-substituted C₃-C₆-cycloalkyl or (but not in the case of    the compounds of the formulae (I-4), (I-6) and (I-7)) in each case    optionally fluorine-, chlorine-, bromine-, C₁-C₄-alkyl-,    C₁-C₂-halogenoalkyl-, C₁-C₄-alkoxy-, C₁-C₂-halogenoalkoxy-, cyano-    or nitro-substituted phenyl or benzyl.-   B particularly preferably represents hydrogen or C₁-C₄-alkyl, or-   A, B and the carbon atom to which they are attached particularly    preferably represent saturated or unsaturated C₅-C₇-cycloalkyl in    which optionally one ring member is replaced by oxygen or sulphur    and which is optionally monosubstituted by C₁-C₆-alkyl,    trifluoromethyl or C₁-C₆-alkoxy, or-   A, B and the carbon atom to which they are attached particularly    preferably represent C₅-C₆-cycloalkyl which is substituted by an    alkylenediyl group which optionally contains one or two not directly    adjacent oxygen and/or sulphur atoms and which is optionally methyl-    or ethyl-substituted, or by an alkylenedioxyl group or by an    alkylenedithiol group which, together with the carbon atom to which    it is attached, forms a further 5- or 6-membered ring, or-   A, B and the carbon atom to which they are attached particularly    preferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which    two substituents together with the carbon atoms to which they are    attached represent in each case optionally C₁-C₂-alkyl- or    C₁-C₂-alkoxy-substituted C₂-C₄-alkanediyl, C₂-C₄-alkenediyl or    butadienediyl.-   D particularly preferably represents hydrogen, represents in each    case optionally fluorine-substituted C₁-C₆-alkyl, C₃-C₆-alkenyl,    C₁-C₄-alkoxy-C₂-C₃-alkyl, represents optionally C₁-C₄-alkyl-,    C₁-C₄-alkoxy- or C₁-C₂-halogenoalkyl-substituted C₃-C₆-cycloalkyl in    which optionally one methylene group is replaced by oxygen or (but    not in the case of the compounds of the formula (I-1)) represents    phenyl or pyridyl, each of which is optionally mono- or    disubstituted by substituents selected from the group consisting of    fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,    C₁-C₄-alkoxy and C₁-C₄-halogenoalkoxy, or-   A and D together particularly preferably represent optionally    substituted C₃-C₅-alkanediyl in which one methylene group may be    replaced by a carbonyl group (but not in the case of the compounds    of the formula (I-1)), by oxygen or by sulphur, possible    substituents being C₁-C₂-alkyl, or-   A and D (in the case of the compounds of the formula (I-1)) together    with the atoms to which they are attached represent one of the    groups AD-1 to AD-10:

-   -   or

-   A and Q¹ together particularly preferably represent C₃-C₄-alkanediyl    which is optionally mono- or disubstituted by identical or different    substituents selected from the group consisting of C₁-C₂-alkyl and    C₁-C₂-alkoxy, or

-   Q¹ particularly preferably represents hydrogen.

-   Q² particularly preferably represents hydrogen.

-   Q⁴, Q⁵ and Q⁶ independently of one another each particularly    preferably represent hydrogen or C₁-C₃-alkyl.

-   Q³ particularly preferably represents hydrogen, C₁-C₄-alkyl or    represents C₃-C₆-cycloalkyl which is optionally mono- or    disubstituted by methyl or methoxy, or

-   Q³ and Q⁴ together with the carbon to which they are attached    particularly preferably represent an optionally C₁-C₂-alkyl- or    C₁-C₂-alkoxy-substituted saturated C₅-C₆-membered ring in which    optionally one ring member is replaced by oxygen or sulphur.

-   G particularly preferably represents hydrogen (a) or represents one    of the groups

in particular (a), (b) or (c),

-   -   in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.

-   R¹ particularly preferably represents in each case optionally    fluorine- or chlorine-substituted C₁-C₈-alkyl, C₂-C₈-alkenyl,    C₁-C₄-alkoxy-C₁-C₂-alkyl, C₁-C₄-alkylthio-C₁-C₂-alkyl or optionally    fluorine-, chlorine-, C₁-C₂-alkyl- or C₁-C₂-alkoxy-substituted    C₃-C₆-cycloalkyl in which optionally one or two not directly    adjacent ring members are replaced by oxygen,    -   represents phenyl which is optionally mono- or disubstituted by        fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl,        C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl or C₁-C₂-halogenoalkoxy,

-   R² particularly preferably represents in each case optionally    fluorine-substituted C₁-C₈-alkyl, C₂-C₈-alkenyl or    C₁-C₄-alkoxy-C₂-C₄-alkyl,    -   represents optionally C₁-C₂-alkyl- or C₁-C₂-alkoxy-substituted        C₃-C₆-cycloalkyl or    -   represents phenyl or benzyl, each of which is optionally        monosubstituted by fluorine, chlorine, bromine, cyano, nitro,        C₁-C₄-alkyl, C₁-C₃-alkoxy, trifluoromethyl or trifluoromethoxy.

-   R³ particularly preferably represents optionally    fluorine-substituted C₁-C₆-alkyl or represents phenyl which is    optionally monosubstituted by fluorine, chlorine, bromine,    C₁-C₄-alkyl, C₁-C₄-alkoxy, trifluoromethyl, trifluoro-methoxy, cyano    or nitro,

-   R⁴ particularly preferably represents C₁-C₆-alkyl, C₁-C₆-alkoxy,    C₁-C₆-alkyl-amino, di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio,    C₃-C₄-alkenylthio, C₃-C₆-cycloalkylthio or represents phenyl,    phenoxy or phenylthio, each of which is optionally monosubstituted    by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy,    C₁-C₃-halogenoalkoxy, C₁-C₃-alkylthio, C₁-C₃-halogenoalkylthio,    C₁-C₃-alkyl or trifluoromethyl.

-   R⁵ particularly preferably represents C₁-C₆-alkoxy or    C₁-C₆-alkylthio.

-   R⁶ particularly preferably represents hydrogen, C₁-C₆-alkyl,    C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl,    C₁-C₆-alkoxy-C₁-C₄-alkyl, represents phenyl which is optionally    monosubstituted by fluorine, chlorine, bromine, trifluoromethyl,    C₁-C₄-alkyl or C₁-C₄-alkoxy, represents benzyl which is optionally    monosubstituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,    trifluoromethyl or C₁-C₄-alkoxy.

-   R⁷ particularly preferably represents C₁-C₆-alkyl, C₃-C₆-alkenyl or    C₁-C₆-alkoxy-C₁-C₄-alkyl.

-   R⁶ and R⁷ together particularly preferably represent an optionally    methyl- or ethyl-substituted C₅-alkylene radical in which optionally    one methylene group is replaced by oxygen or sulphur.

In the radical definitions mentioned as being particularly preferred,halogen represents fluorine, chlorine, bromine and iodine, and inparticular fluorine, chlorine and bromine.

-   W very particularly preferably represents hydrogen, methyl, ethyl,    i-propyl, vinyl or ethinyl.-   X very particularly preferably represents methyl, ethyl, n-propyl,    iso-propyl, vinyl or ethinyl, Y very particularly preferably    represents hydrogen, methyl, ethyl, i-propyl, vinyl or ethinyl.-   Z very particularly preferably represents hydrogen, methyl, ethyl,    n-propyl, i-butyl, vinyl or ethinyl,    with the proviso that at least one of the radicals W, X, Y or Z    represents a chain having at least two carbon atoms where at most    only one of the radicals W, X, Y or Z may represent vinyl or    ethinyl,

CKE very particularly preferably represents one of the groups

-   A very particularly preferably represents in each case optionally    fluorine-substituted C₁-C₄-alkyl or C₁-C₂-alkoxy-C₁-C₂-alkyl,    cyclopropyl, cyclopentyl or cyclohexyl and, only in the case of the    compounds of the formula (I-5), represents optionally fluorine-,    chlorine-, bromine-, methyl-, ethyl-, n-propyl-, iso-propyl-,    methoxy-, ethoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or    nitro-substituted phenyl.-   B very particularly preferably represents hydrogen, methyl or ethyl,    or-   A, B and the carbon atom to which they are attached very    particularly preferably represent saturated C₅-C₆-cycloalkyl in    which optionally one ring member is replaced by oxygen or sulphur    and which is optionally monosubstituted by methyl, ethyl, propyl,    isopropyl, trifluoromethyl, methoxy, ethoxy, propoxy or butoxy or-   A, B and the carbon atom to which they are attached very    particularly preferably represent C₆-cycloalkyl which is substituted    by an alkylenedioxyl group which contains two oxygen atoms which are    not directly adjacent, or-   A, B and the carbon atom to which they are attached represent    C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which two substituents    together with the carbon atoms to which they are attached very    particularly preferably represent C₂-C₄-alkanediyl or    C₁-C₄-alkenediyl or butadienediyl.-   D very particularly preferably represents hydrogen, represents in    each case optionally fluorine-substituted C₁-C₄-alkyl,    C₃-C₄-alkenyl, C₁-C₄-alkoxy-C₂-C₃-alkyl, cyclopropyl, cyclopentyl or    cyclohexyl or (but not in the case of the compounds of the formula    (I-1)) represents pyridyl or phenyl which is optionally    monosubstituted by fluorine, chlorine, methyl, ethyl, n-propyl,    iso-propyl, methoxy, ethoxy or trifluoromethyl,    or-   A and D together very particularly preferably represent optionally    substituted C₃-C₄-alkanediyl in which optionally one carbon atom is    replaced by oxygen or sulphur-   A and Q¹ together very particularly preferably represent    C₃-C₄-alkanediyl which is optionally mono- or disubstituted by    methyl or methoxy, or-   Q¹ very particularly preferably represents hydrogen.-   Q² very particularly preferably represents hydrogen.-   Q⁴, Q⁵ and Q⁶ independently of one another each very particularly    preferably represent hydrogen or methyl.-   Q³ very particularly preferably represents hydrogen, methyl, ethyl    or propyl, or-   Q³ and Q⁴ together with the carbon to which they are attached very    particularly preferably represent a saturated C₅-C₆-ring which is    optionally monosubstituted by methyl or methoxy.-   G very particularly preferably represents hydrogen (a) or represents    one of the groups

-   -   in which    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.

-   R¹ very particularly preferably represents C₁-C₆-alkyl,    C₂-C₆-alkenyl, C₁-C₂-alkoxy-C₁-alkyl, C₁-C₂-alkylthio-C₁-alkyl or    cyclohexyl or cyclopropyl which is optionally monosubstituted by    fluorine, chlorine, methyl or methoxy,    -   represents phenyl which is optionally monosubstituted by        fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy,        trifluoromethyl or trifluoromethoxy,

-   R² very particularly preferably represents in each case optionally    fluorine-substituted C₁-C₈-alkyl, C₂-C₆-alkenyl or    C₁-C₄-alkoxy-C₂-C₃-alkyl, phenyl or benzyl.

-   W most particularly preferably represents hydrogen, methyl, ethyl or    i-propyl,

-   X most particularly preferably represents methyl, ethyl, i-propyl or    vinyl,

-   Y most particularly preferably represents hydrogen, methyl, ethyl,    i-propyl, vinyl or ethinyl,

-   Z most particularly preferably represents hydrogen, methyl, ethyl,    n-propyl or i-butyl,    with the proviso that at least one of the radicals W, X, Y or Z    represents a chain having at least two carbon atoms, where at most    only one of the radicals W, X, Y or Z may represent vinyl or    ethinyl,

CKE most particularly preferably represents one of the groups

-   A most particularly preferably represents methyl,-   B most particularly preferably represents methyl,-   A, B and the carbon atoms to which they are attached most    particularly preferably represent saturated C₅-C₆-cycloalkyl in    which optionally one ring member is replaced by oxygen and which is    optionally monosubstituted by methyl, ethyl, methoxy, ethoxy.-   A and B together represent

-   D most particularly preferably represents hydrogen or (but not in    the case of the compound of the formula (I-1)) represents    fluorine-substituted phenyl,-   G most particularly preferably represents hydrogen (a) or represents    one of the groups

-   R¹ most particularly preferably represents C₁-C₆-alkyl,    C₁-C₂-alkoxymethyl,-   R² most particularly preferably represents C₁-C₄-alkyl.

For CKE=(6)

-   A and Q¹ together most particularly preferably represent    C₃-C₄-alkanediyl and-   B and Q² each most particularly preferably represent hydrogen.

The abovementioned general or preferred radical definitions orillustrations can be combined with each other as desired, i.e. includingcombinations between the respective ranges and preferred ranges. Theyapply both to the end products and, correspondingly, to the precursorsand intermediates.

Preference according to the invention is given to the compounds of theformula (I) which contain a combination of the meanings listed above asbeing preferred (preferable).

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

Most preference according to the invention is given to the compounds ofthe formula (I) which contain a combination of the meanings listed aboveas being most preferred.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenylmay in each case be straight-chain or branched as far as this ispossible, including in combination with heteroatoms, such as, forexample, in alkoxy.

Unless stated otherwise, optionally substituted radicals may be mono- orpolysubstituted and, in the case of polysubstitutions, the substituentsmay be identical or different.

Besides the compounds mentioned in the Preparation Examples, thefollowing compounds of the formula (I-1-a) may be specificallymentioned:

TABLE 1

W = CH₃, X = CH₃, Y = C≡CH, Z = H. A B D CH₃ H H C₂H₅ H H C₃H₇ H Hi-C₃H₇ H H C₄H₉ H H i-C₄H₉ H H s-C₄H₉ H H t-C₄H₉ H H CH₃ CH₃ H C₂H₅ CH₃H C₃H₇ CH₃ H i-C₃H₇ CH₃ H C₄H₉ CH₃ H i-C₄H₉ CH₃ H s-C₄H₉ CH₃ H t-C₄H₉CH₃ H C₂H₅ C₂H₅ H C₃H₇ C₃H₇ H

CH₃ H

CH₃ H

CH₃ H —(CH₂)₂— H —(CH₂)₄— H —(CH₂)₅— H —(CH₂)₆— H —(CH₂)₇— H—(CH₂)₂—O—(CH₂)₂— H —CH₂—O—(CH₂)₃— H —(CH₂)₂—S—(CH₂)₂— H—CH₂—CHCH₃—(CH₂)₃— H —(CH₂)₂—CHCH₃—(CH₂)₂— H —(CH₂)₂—CHC₂H₅—(CH₂)₂— H—(CH₂)₂—CHC₃H₇—(CH₂)₂— H —(CH₂)₂—CHi—C₃H₇—(CH₂)₂— H—(CH₂)₂—CHOCH₃—(CH₂)₂— H —(CH₂)₂—CHOC₂H₅—(CH₂)₂— H—(CH₂)₂—CHOC₃H₇—(CH₂)₂— H —(CH₂)₂—CHi—C₃H₇—(CH₂)₂— H—(CH₂)₂—C(CH₃)₂—(CH₂)₂— H —CH₂—(CHCH₃)₂—(CH₂)₂— H

H

H

H

H

H —(CH₂)₃— H —(CH₂)₄— H —CH₂—CHCH₃—CH₂— H —CH₂—CH₂—CHCH₃— H—CH₂—CHCH₃—CHCH₃— H —CH₂—S—CH₂— H —CH₂—S—(CH₂)₂— H

H H CH₃ H H C₂H₅ H H C₃H₇ H H i-C₃H₇ H H

H H

H H

H CH₃ CH₃ H CH₃ C₂H₅ H CH₃ C₃H₇ H CH₃ i-C₃H₇ H CH₃

H CH₃

H CH₃

H C₂H₅ CH₃ H C₂H₅ C₂H₅ HTable 2: A, B and D are each as given in Table 1

-   -   W═CH₃; X═CH₃; Y═CH═CH₂; Z═H.        Table 3: A, B and D are each as given in Table 1    -   W═CH₃; X═C₂H₅; Y═CH₃; Z═H.        Table 4: A, B and D are each as given in Table 1    -   W═CH₃; X═CH₃; Y═C₂H₅; Z═H.        Table 5: A, B and D are each as given in Table 1    -   W═C₂H₅; X═C₂H₅; Y═CH₃; Z═H.        Table 6: A, B and D are each as given in Table 1    -   W═C₂H₅; X═C₂H₅; Y═C₂H₅; Z═H.        Table 7: A, B and D are each as given in Table 1    -   W═CH₃; X═C≡CH; Y═CH₃; Z═H.        Table 8: A, B and D are each as given in Table 1    -   W═CH₃; X═CH═CH₂; Y═CH₃; Z═H.        Table 9: A, B and D are each as given in Table 1    -   W═CH₃; X═C₂H₅; Y═C₂H₅; Z═H.        Table 10: A, B and D are each as given in Table 1    -   W═H; X═CH₃; Y═C≡CH; Z═H.        Table 11: A, B and D are each as given in Table 1    -   W═H; X═CH₃; Y═CH═CH; Z═H.        Table 12: A, B and D are each as given in Table 1    -   W═H; X═C₂H₅; Y═CH₃; Z═H.        Table 13: A, B and D are each as given in Table 1    -   W═H; X═CH₃; Y═C₂H₅; Z═H.        Table 14: A, B and D are each as given in Table 1    -   W═H; X═CH₃; Y═H; Z═C₂H₅.        Table 15: A, B and D are each as given in Table 1    -   W═H; X═CH₃; Y═CH₃; Z═C₂H₅.

Besides the compounds mentioned in the Preparation Examples, thefollowing compounds of the formula (I-2-a) may be specificallymentioned:

TABLE 16

W = CH₃, X = CH₃, Y = C≡CH, Z = H A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃ CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉ CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——CH₂—O—(CH₂)₃— —(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃——(CH₂)₂—CHCH₃—(CH₂)₂— (CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂——(CH₂)₂—CHi—C₃H₇—(CH₂)₂— —(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂——(CH₂)₂—CHOC₃H₇—(CH₂)₂— —(CH₂)₂—CHi—C₃H₇—(CH₂)₂— —(CH₂)₂—C(CH₃)₂—(CH₂)₂——CH₂—(CHCH₃)₂—(CH₂)₂—

Table 17: A and B are each as given in Table 16

-   -   W═CH₃; X═CH₃; Y═CH═CH₁; Z═H.        Table 18: A and B are each as given in Table 16    -   W═CH₃; X═CH₅; Y═CH₃; Z═H.        Table 19: A and B are each as given in Table 16    -   W═CH₃; X═CH₃; Y═C₂H₅; Z═H.        Table 20: A and B are each as given in Table 16    -   W═C₂H₅; X═C₂H₅; Y═CH₃; Z═H.        Table 21: A and B are each as given in Table 16    -   W═C₇H₅; X═C₂H₅; Y═C₂H₅; Z═H.        Table 22: A and B are each as given in Table 16    -   W═CH₃; X═C≡CH; Y═CH₃; Z═H.        Table 23: A and B are each as given in Table 16    -   W═CH₃; X═CH═CH₂; Y═CH₃; Z═H.        Table 24: A and B are each as given in Table 16    -   W═CH₃; X═C₂H₅; Y═C₂H₅; Z═H.        Table 25: A and B are each as given in Table 16    -   W═H; X═CH₃; Y═C≡CH; Z═H.        Table 26: A and B are each as given in Table 16    -   W═H; X═CH₃; Y═CH═CH₂; Z═H.        Table 27: A and B are each as given in Table 16    -   W═H; X═C₂H₅; Y═CH₃; Z═H.        Table 28: A and B are each as given in Table 16    -   W═H; X═CH₃; Y═C₂H₅; Z═H.        Table 29: A and B are each as given in Table 16    -   W═H; X═CH₃; Y═H; Z═C₂H₅.        Table 30: A and B are each as given in Table 16    -   W═H; X═CH₃; Y═CH₃; Z═C₂H₅.

Using, in accordance with process (A), ethylN-(2-methyl-4-ethinyl-phenylacetyl)-1-aminocyclohexane-carboxylate asstarting material, the course of the process according to the inventioncan be represented by the following equation:

Using, in accordance with process (B), ethylO-(2,4,6-triethyl-phenylacetyl)-2-hydroxyisobutyrate, the course of theprocess according to the invention can be represented by the followingequation:

Using, in accordance with process (C), ethyl2-(2,6-dimethyl-4-ethyl-phenyl)-4-(4-methoxy)-benzylmercapto-4-methyl-3-oxo-valerate,the course of the process according to the invention can be representedby the following equation:

Using, for example in accordance with process (D), (chlorocarbonyl)2-(2-ethyl-4,6-dimethyl)-phenylketene and acetone as starting materials,the course of the process according to the invention can be representedby the following equation:

Using, for example in accordance with process (E), (chlorocarbonyl)2-(2,6-dimethyl-4-ethyl)-phenyl ketene and thiobenzamide as startingmaterials, the course of the process according to the invention can berepresented by the following equation:

Using, in accordance with process (F), ethyl5-(2,4-diethyl-6-methyl-phenyl)-2,3-tetramethylene-4-oxo-valerate, thecourse of the process according to the invention can be represented bythe following equation:

Using, in accordance with process (G), ethyl5-[(2,4,6-triethyl-phenyl)-phenyl]-2,2-dimethyl-5-oxo-hexanoate, thecourse of the process according to the invention can be represented bythe following equation:

Using, in accordance with process (H),3-[(2,6-dimethyl-4-bromo)-phenyl]-4,4-(pentamethylene)-pyrrolidine-2,4-dioneas starting material, the course of the reaction can be represented bythe following scheme:

Using, in accordance with process (Iα),3-(2,6-dimethyl-4-ethinyl-phenyl)-5,5-dimethylpyrrolidine-2,4-dione andpivaloyl chloride as starting materials, the course of the processaccording to the invention can be represented by the following equation:

Using, in accordance with process (Iβ),3-(2-ethyl-4,6-dimethyl-phenyl)-4-hydroxy-5-phenyl-Δ³-dihydrofuran-2-oneand acetic anhydride as starting materials, the course of the processaccording to the invention can be represented by the following equation:

Using, in accordance with process (J),8-[(2,6-diethyl-4-methyl)-phenyl]-1-aza-bicyclo-[4.3.0^(1,6)]-nonane-7,9-dioneand ethoxyethyl chloroformate as starting materials, the course of theprocess according to the invention can be represented by the followingequation:

Using, in accordance with process (K),3-(2-ethyl-4,6-dimethyl-phenyl)-4-hydroxy-5-methyl-6-(3-pyridyl)-pyroneand methyl chloromonothioformate as starting materials, the course ofthe reaction can be represented as follows:

Using, in accordance with process (L),3-(2,6-dimethyl-4-ethyl-phenyl)-5,5-penta-methylene-pyrrolidine-2,4-dioneand methanesulfonyl chloride as starting materials, the course of thereaction can be represented by the following equation:

Using, in accordance with process (M),3-(2,4-diethyl-6-methyl-phenyl)-4-hydroxy-5,5-dimethyl-Δ³-dihydrofuran-2-oneand 2,2,2-trifluoroethyl methanethio-phosphonyl chloride as startingmaterials, the course of the reaction can be represented by thefollowing equation:

Using, in accordance with process (N),3-(2,4,6-triethyl-phenyl)-5-cyclopropyl-5-methyl-pyrrolidine-2,4-dioneand NaOH as components, the course of the process according to theinvention can be represented by the following equation:

Using, in accordance with process (O), variant α,3-(2,4-diethyl-6-methyl-phenyl)-4-hydroxy-5-tetramethylene-Δ³-dihydro-furan-2-oneand ethyl isocyanate as starting materials, the course of the reactioncan be represented by the following equation:

Using, in accordance with process (O), variant B,3-(4-ethinyl-2,6-dimethyl-phenyl)-5-methyl-pyrrolidine-2,4-dione anddimethylcarbamoyl chloride as starting materials, the course of thereaction can be represented by the following scheme:

The compounds of the formula (II)

in which

A, B, D, W, X, Y, Z and R⁸ are each as defined above

which are required as starting materials in the process (a) according tothe invention are novel.

The acylamino acid esters of the formula (II) are obtained, for example,when amino acid derivatives of the formula (XXI)

in which

A, B, R⁸ and D are each as defined above

are acylated with substituted phenylacetyl halides of the formula (XXII)

in which

W, X, Y and Z are each as defined above and

Hal represents chlorine or bromine

-   (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6,    341-5, 1968)    or when acylamino acids of the formula (XXIII)

in which

A, B, D, W, X, Y and Z are each as defined above are esterified (Chem.Ind. (London) 1568 (1968)).

The compounds of the formula (XXIII)

in which

A, B, D, W, X, Y and Z are each as defined above

are novel.

Compounds of the formula (XXIII) are obtained when amino acids of theformula (XXIV)

in which

A, B and D are each as defined above

are acylated with substituted phenyl acetyl halides of the formula(XXII)

in which

W, X, Y and Z are each as defined above and

Hal represents chlorine or bromine,

for example according to Schotten-Baumann (Organikum, VEB DeutscherVerlag der Wissenschaften, Berlin 1977, p. 505).

The compounds of the formula (XXII) are novel. They can be prepared byprocesses which are known in principle (see, for example, H. Henecka,Houben-Weyl, Methoden der Organischen Chemie, Vol. 8, pp. 467-469(1952)).

The compounds of the formula (XXII) are obtained, for example, byreacting substituted phenylacetic acids of the formula (XXV)

in which

W, X, Y and Z are each as defined above

with halogenating agents (for example thionyl chloride, thionyl bromide,oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromideor phosphorus pentachloride), if appropriate in the presence of adiluent (for example optionally chlorinated aliphatic or aromatichydrocarbons such as toluene or methylene chloride), at temperaturesfrom −20° C. to 150° C., preferably from −10° C. to 100° C.

Some of the compounds of the formulae (XXI) and (XXIV) are known, and/orthey can be prepared by known processes (see, for example, Compagnon,Miocque Ann. Chim. (Paris) [14] 5, S. 11-22, 23-27 (1970)).

The substituted cyclic aminocarboxylic acids of the formula (XXIV) inwhich A and B form a ring are generally obtainable by the Bucherer-Bergssynthesis or by the Strecker synthesis and are in each case obtained indifferent isomer forms. Thus, under the conditions of the Bucherer-Bergssynthesis, the isomers (for simplicity called B below), in which theradicals R and the carboxyl group are equatorial are predominantlyobtained, while under the conditions of the Strecker synthesis theisomers (for simplicity called (o below) in which the amino group andthe radicals R are equatorial are predominantly obtained.

-   (L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri,    Can. J. Chem. 53, 3339 (1975).

Furthermore, the starting materials of the formula (II)

in which

A, B, D, W, X, Y, Z and R⁸ are each as defined above

used in the above process (A) can be prepared when aminonitriles of theformula (XXVI)

in which

A, B and D are each as defined above

are reacted with substituted phenylacetyl halides of the formula (XXII)

in which

W, X, Y, Z and Hal are each as defined above

to give compounds of the formula (XXVII)

in which

A, B, D, W, X, Y and Z are each as defined above

and these are subsequently subjected to acidic alcoholysis.

The compounds of the formula (XXVII) are likewise novel.

The compounds of the formula (III)

in which

A, B, W, X, Y, Z and R⁸ are each as defined above

required as starting materials in the process (B) according to theinvention are novel.

They can be prepared by methods known in principle.

Thus, the compounds of the formula (III), for example, are obtained when

2-hydroxycarboxylic esters of the formula (XXVIII)

in which

A, B and R⁸ are each as defined above

are acylated with substituted phenylacetyl halides of the formula (XXII)

in which

W, X, Y, Z and Hal are each as defined above

-   (Chem. Reviews 52, 237-416 (1953)).

Furthermore, compounds of the formula (I) are obtained when substitutedphenylacetic acids of the formula (XXV)

in which

W, X, Y and Z are each as defined above

are alkylated with α-halogenocarboxylic esters of the formula (XXIX)

in which

A, B and R⁸ are each as defined above and

Hal represents chlorine or bromine.

The compounds of the formula (XXV) are novel.

The compounds of the formula (XXIX) are commercially available.

The compounds of the formula (XXV)

in which

W, X, Y and Z are each as defined above

and

Y may furthermore represent —C═C—Si(CH₃)₃

are obtained, for example,

when phenylacetic esters of the formula (XXX)

in which

W, X, Y, Z and R⁸ are each as defined above

are hydrolysed in the presence of acids or bases, in the presence of asolvent, under generally known standard conditions.

The compounds of the formula (XXX) are novel.

The compounds of the formula (XXX)

in which

W, X, Y, Z and R⁸ are each as defined above,

and

Y may furthermore represent —C≡C—Si(CH₃)₃

are obtained, for example,

when phenylacetic esters of the formula (XXX-a)

in which

R⁸, W, X, Y and Z are each as defined above,

and one or two of the radicals, in particular one radical, W, X, Y or Zrepresents chlorine, bromine or iodine, in particular bromine, with theproviso that the other radicals W, X, Y or Z do not represent alkenyl oralkinyl,

are reacted with silylacetylenes of the formula (X-a) or vinylstannanesof the formula (X-b)

in which Alk preferably represents C₁-C₄-alkyl,

R²¹ preferably represents C₁-C₄-alkyl or phenyl and

R²² is as defined above

in the presence of a solvent, if appropriate in the presence of a baseand a catalyst (preferably one of the palladium complexes mentionedabove).

Some of the phenylacetic esters of the formula (XXX-a) are known fromthe applications WO 96/35 664, WO 97/02 243, WO 97/01535, WO 97/36868 orWO 98/05638, or they can be prepared by processes described therein.

Furthermore, phenylacetic esters of the formula (XXX) are obtained bythe processes (P) and (Q) described further below.

The compounds of the formula (IV)

in which

A, B, V, W, X, Y, Z and R⁸ are each as defined above required asstarting materials in the above process (C) are novel.

They can be prepared by methods known in principle.

The compounds of the formula (IV) are obtained, for example whensubstituted phenylacetic esters of the formula (XXX)

in which

W, X, Y, R⁸ and Z are each as defined above are acylated with2-benzylthio-carbonyl halides of the formula (XXX)

in which

A, B and V are each as defined above and

Hal represents halogen (in particular chlorine or bromine) in thepresence of strong bases (see, for example, M. S. Chambers, E. J.Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228).

Some of the benzylthio-carbonyl halides of the formula (XXXI) are known,and/or they can be prepared by known processes (J. Antibiotics (1983),26, 1589). The halogenocarbonyl ketenes of the formula (VI) required asstarting materials in the above process (D) and (E) are novel. They canbe prepared in a simple manner by methods which are known in principle(cf. for example, Org. Prep. Proced. Int., 7, (4), 155-158, 1975 and DE1 945 703). Thus, for example, the compounds of the formula (VI)

in which

W, X, Y and Z are each as defined above and

Hal represents chlorine or bromine

are obtained when substituted phenylmalonic acids of the formula (XXXII)

in which

W, X, Y and Z are each as defined above

are reacted with acid halides, such as, for example, thionyl chloride,phosphorus(V) chloride, phosphorus(III) chloride, oxalyl chloride,phosgene or thionyl bromide, if appropriate in the presence ofcatalysts, such as, for example, diethylformamide,methyl-sterylformamide or triphenylphosphine and, if appropriate, in thepresence of bases, such as, for example, pyridine or triethylamine.

The substituted phenylmalonic acids of the formula (XXXII) are novel.They can be prepared in a simple manner by known processes (cf., forexample, Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin1977, p. 517 ff, EP-A-528 156, WO 96/35 664, WO 97/02 243, WO 97/01535,WO 97/36868 and WO 98/05638).

Thus, phenylmalonic acids of the formula (XXXII)

in which

W, X, Y and Z are each as defined above are obtained when phenylmalonicesters of the formula (XXXIII)

in which

W, X, Y, Z and R⁸ are each as defined above are initially hydrolysed inthe presence of a base and a solvent and subsequently carefullyacidified (EP-528 156, WO 96/35 664, WO 97/02 243).

Some of the malonic esters of the formula (XXXIII)

in which

W, X, Y, Z and R⁸ are each as defined above

are known.

They can be prepared by generally known methods of organic chemistry(cf., for example, Tetrahedron Lett. 27, 2763 (1986), Organikum, VEBDeutscher Verlag der Wissenschaften, Berlin 1977, p. 587 ff., WO96/35664, WO 97/02243, WO 97/01535, WO 97/36868, WO 98/05638 and WO99/47525).

The carbonyl compounds of the formula (V)

in which

A and D are each as defined above required as starting materials for theprocess (D) according to the invention or their silyl enol ethers of theformula (Va)

in which

A, D and R⁸ are each as defined above

are commercially available, generally known compounds or compounds whichare obtainable by known processes.

The preparation of the ketene acid chlorides of the formula (VI)required as starting materials for carrying out the process (E)according to the invention has already been described above. Thethioamides of the formula (VII)

in which

A is as defined above

required for carrying out the process (E) according to the invention arecompounds which are generally known in organic chemistry.

The compounds of the formula (VI)

in which

A, B, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above

required as starting materials in the above process (F) are novel.

They can be prepared by methods known in principle.

The 5-aryl-4-ketocarboxylic esters of the formula (VIII) are obtained,for example, when 5-aryl-4-ketocarboxylic acids of the formula (XXXIV)

in which

W, X, Y, Z, A, B, Q¹ and Q² are each as defined above are esterified(cf., for example, Organikum, 15^(th) edition, Berlin, 1977, page 499)or alkylated (see Preparation Example).

The 5-aryl-4-ketocarboxylic acids of the formula (XXXIV)

in which

A, B, Q¹, Q², W, X, Y and Z are each as defined above

are novel but can be prepared by methods known in principle (seePreparation Example).

The 5-aryl-4-ketocarboxylic acids of the (XXXIV) are obtained, forexample, when 2-phenyl-3-oxo-adipic esters of the formula (XXXV)

in which

A, B, D¹, D², W, X, Y and Z are each as defined above and

R⁸ and R^(8′) each represent alkyl (in particular C₁-C₈-alkyl) and inwhich, if the compound of the formula (XXXVII) is used, R⁸ representshydrogen

are decarboxylated, if appropriate in the presence of a diluent and ifappropriate in the presence of a base or an acid (cf., for example,Organikum, 15^(th) edition, Berlin, 1977, pages 519 to 521).

The compounds of the formula (XXXV)

in which

A, B, Q¹, Q², W, X, Y, Z, R⁸, R^(8′) are each as defined above and inwhich, if the compound of the formula (XXXVII) is used, R⁸ representshydrogen

are novel.

The compounds of the formula (XXXV) are obtained, for example,

when dicarboxylic monoester chlorides of the formula (XXXVI),

in which

A, B, Q¹, Q² and R⁸ are each as defined above and

Hal represents chlorine or bromine

or carboxylic anhydrides of the formula (XXXVII)

in which

A, B, Q¹ and Q² are each as defined above are acylated with aphenylacetic ester of the formula (XXX)

in which

W, X, Y, Z and R^(8′) are each as defined above in the presence of adiluent and in the presence of a base (cf., for example, M. S. Chambers,E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228,cf. also the Preparation Examples).

Some of the compounds of the formulae (XXXVI) and (XXXVII) are knowncompounds of organic chemistry, and/or they can be prepared in a simplemanner by methods known in principle.

The compounds of the formula (IX)

in which

A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y, Z and R⁸ are each as defined above

required as starting materials in the above process (G) are novel.

They can be prepared by methods known in principle.

The 6-aryl-5-ketocarboxylic esters of the formula (IX) are obtained, forexample, when 6-aryl-5-ketocarboxylic acids of the formula (XXXVIII)

in which

A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as defined above

are esterified (cf., for example, Organikum, 15^(th) edition, Berlin,1977, page 499).

The 6-aryl-5-ketocarboxylic acids of the formula (XXXVIII)

in which

A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as defined above

are novel. They can be prepared by methods known in principle, forexample by hydrolysing and decarboxylating

substituted 2-phenyl-3-oxo-heptanedioic esters of the formula (XXXIX)

in which

A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y and Z are each as defined above and

R⁸ and R^(8′) are each alkyl (preferably C₁-C₆-alkyl),

if appropriate in the presence of a diluent and if appropriate in thepresence of a base or acid (cf., for example, Organikum, 15^(th)edition, Berlin, 1977, pages 519 to 521).

The compounds of the formula (XXXIX)

in which

A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y, Z, R⁸ and R^(8′) are each as definedabove are novel and can be obtained when dicarboxylic anhydrides of theformula (XLI)

in which

A, B, Q³, Q⁴, Q⁵, Q⁶ and R⁸ are each as defined above are condensed witha substituted phenylacetic ester of the formula (XXX)

in which

W, X, Y, Z and R^(8′) are each as defined above

in the presence of a diluent and in the presence of a base.

Some of the compounds of the formula (XLI) are known, and/or they can beprepared by known processes.

The compounds of the formula (XXX) have already been described under theprecursors for the process (B) or are described explicitly as examplesin processes (P) and (Q) below.

(P) Thus, furthermore, compounds of the formula (XXX),

in which

W, X, Y, Z and R^(8′) are each as defined above are obtained whenacylphenylacetic esters of the formula (XLII)

W, X, Y and R⁸ are each as defined above and

Z′ represents alkyl are reduced with suitable reducing agents (such as,for example, Zn/HCl, hydrogen/catalyst, hydrazine/base), if appropriatein the presence of a solvent.

The compounds of the formula (XLII) are novel.

Compounds of the formula (XLII)

in which

W, X, Y, Z′ and R^(8′) are each as defined above are obtained whenphenylacetic esters of the formula (XXX-b)

in which

W, X, Y and R^(8′) are each as defined above and

Z represents hydrogen are Friedel-Crafts acylated, if appropriate in thepresence of a solvent, using a carbonyl chloride or carboxylic anhydridein the presence of an acid or a Lewis acid (for example aluminiumchloride, iron(III) bromide).

The compounds (XXX-b) are known or can be prepared by the processesdescribed in the literature cited at the outset.

(Q) Phenylacetic esters of the formula (XXX),

in which

X represents alkyl,

W, Y and Z each represent hydrogen or alkyl and

R^(8′) represents alkyl are furthermore obtained when phenylaceticesters of the formula (XXX-c),

in which

X represents alkyl,

R^(8′) represents alkyl and

W, Y and Z may represent, in addition to hydrogen and alkyl, chlorineand bromine

are dehalogenated in the presence of a solvent and in the presence of areducing agent (for example hydrogen in the presence of a noble-metalcatalyst such as, for example, palladium or platinum).

The compounds of the formula (XXX-c) are known from the patentapplications cited at the outset or can be prepared by the processesdescribed therein.

Some of the compounds of the formulae (I-1′a) to (I-8′-a) in which A, B,D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W′, X′, Y′ and Z′ are each as defined above,required as starting materials in the above process (H), are known (WO96/35 664, WO 97/02 243, WO 97/01535, WO 97/36868, WO 98/05638) or theycan be prepared by the processes described therein.

Some of the coupling agents of the formulae (X-a) and (X-b)

in which

Alk, R²¹ and R²² are each as defined above

are commercially available, or they can be prepared in a simple mannerby generally known processes.

The acid halides of the formula (XI), carboxylic anhydrides of theformula (XII), chloroformic esters or chloroformic thioesters of theformula (XIII), chloromonothioformic esters or chlorodithioformic estersof the formula (XIV), sulphonyl chlorides of the formula (XV),phosphorus compounds of the formula (XVI) and metal hydroxides, metalalkoxides or amines of the formulae (XVII) and (XVII) and isocyanates ofthe formula (XIX) and carbamoyl chlorides of the formula (XX)furthermore required as starting materials for carrying out theprocesses (I), (J), (K), (L), (M), (N) and (O) according to theinvention are generally known compounds of organic or inorganicchemistry.

Moreover, the compounds of the formulae (V), (VII), (XI) to (XX), (XXI),(XXIV), (XXVI), (XXVIII), (XXIX), (XXXI), (XXXVI), (XXXVII) and (XLI)are known from the patent applications cited at the outset, and/or theycan be prepared by the methods given therein.

The process (A) is characterized in that compounds of the formula (II)in which A, B, D, W, X, Y, Z and R⁸ are each as defined above aresubjected to an intramolecular condensation in the presence of a base.

Suitable diluents for the process (A) according to the invention are allinert organic solvents. Preference is given to using hydrocarbons, suchas toluene and xylene, furthermore ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methyl-pyrrolidone, and also alcohols, such asmethanol, ethanol, propanol, iso-propanol, butanol, iso-butanol andtert-butanol.

Suitable bases (deprotonating agents) for carrying out the process (A)according to the invention are all customary proton acceptors.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be employed in thepresence of phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium andpotassium can also be used. Furthermore, alkali metal and alkaline earthmetal amides and hydrides, such as sodium amide, sodium hydride andcalcium hydride, and additionally also alkali metal alkoxides, such assodium methoxide, sodium ethoxide and potassium tert-butoxide can beemployed.

When carrying out the process (A) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures between 0° C. and250° C., preferably between 50° C. and 150° C.

The process (A) according to the invention is generally carried outunder atmospheric pressure.

When carrying out process (A) according to the invention, the reactioncomponents of the formula (II) and the deprotonating bases are generallyemployed in approximately double-equimolar amounts. However, it is alsopossible to use a larger excess (up to 3 mol) of one component or theother.

The process (B) is characterized in that compounds of the formula (III)in which A, B, W, X, Y, Z and R⁸ are each as defined above are subjectedto an intramolecular condensation in the presence of a diluent and inthe presence of a base.

Suitable diluents for the process (B) according to the invention are allinert organic solvents. Preference is given to using hydrocarbons, suchas toluene and xylene, furthermore ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methyl-pyrrolidone, and also alcohols, such asmethanol, ethanol, propanol, iso-propanol, butanol, iso-butanol andtert-butanol.

Suitable bases (deprotonating agents) for carrying out the process (B)according to the invention are all customary proton acceptors.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be employed in thepresence of phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium andpotassium can also be used. Furthermore, alkali metal and alkaline earthmetal amides and hydrides, such as sodium amide, sodium hydride andcalcium hydride, and additionally also alkali metal alkoxides, such assodium methoxide, sodium ethoxide and potassium tert-butoxide can beemployed.

When carrying out the process (B) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures between 0° C. and250° C., preferably between 50° C. and 150° C.

The process (B) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (B) according to the invention, thereaction components of the formula (III) and the deprotonating bases aregenerally employed in approximately equimolar amounts. However, it isalso possible to use a relatively large excess (up to 3 mol) of onecomponent or the other.

The process (C) is characterized in that compounds of the formula (IV)in which A, B, V, W, X, Y, Z and R⁸ are each as defined above arecyclized intramolecularly in the presence of an acid and, ifappropriate, in the presence of a diluent.

Suitable diluents for the process (C) according to the invention are allinert organic solvents. Preference is given to using hydrocarbons, suchas toluene and xylene, furthermore halogenated hydrocarbons such asdichloromethane, chloroform, ethylene chloride, chlorobenzene,dichlorobenzene, moreover polar solvents, such as dimethyl sulphoxide,sulpholane, dimethyl formamide and N-methyl-pyrrolidone. Furthermore, itis possible to employ alcohols such as methanol, ethanol, propanol,iso-propanol, butanol, isobutanol and tert-butanol.

If appropriate, the acid used can also serve as diluent.

Suitable acids for the process (C) according to the invention are allcustomary inorganic and organic acids, such as, for example, hydrohalicacids, sulphuric acid, alkyl-, aryl- and haloalkylsulphonic acids, inparticular halogenated alkylcarboxylic acids, such as, for example,trifluoroacetic acid.

When carrying out the process (C) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures between 0° C. and250° C., preferably between 50° C. and 150° C.

The process (C) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (C) according to the invention, thereaction components of the formulae (IV) and the acid are employed, forexample, in equimolar amounts. However, it is also possible, ifappropriate, to use the acid as solvent or as catalyst.

The process (D) according to the invention is characterized in thatcarbonyl compounds of the formula (V) or enol ethers thereof of theformula (V-a) are reacted with ketene acid halides of the formula (VI)in the presence of a diluent and, if appropriate, in the presence of anacid acceptor.

Suitable diluents for the process (D) according to the invention are allinert organic solvents. Preference is given to using hydrocarbons, suchas toluene and xylene, furthermore ethers, such as dibutyl ether, glycoldimethyl ether and diglycol dimethyl ether, moreover polar solvents,such as dimethyl sulphoxide, sulpholane, dimethylformamide orN-methyl-pyrrolidone.

Suitable acid acceptors for carrying out the process variant D)according to the invention are all customary acid acceptors.

Preference is given to using tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU),diazabicyclononene (DBN), Hünig base and N,N-dimethyl-aniline.

When carrying out the process variant D) according to the invention, thereaction temperatures can be varied within a relatively wide range.Advantageously, the reaction is carried out at temperatures between 0°C. and 250° C., preferably between 50° C. and 220° C.

The process (D) according to the invention is advantageously carried outunder atmospheric pressure.

When carrying out the process (D) according to the invention, thereaction components of the formulae (V) and (VI) in which A, D, W, X, Yand Z are each as defined above and Hal represents halogen, and, ifappropriate, the acid acceptors, are generally employed in approximatelyequimolar amounts. However, it is also possible to use a relativelylarge excess (up to 5 mol) of one component or the other.

The process (E) according to the invention is characterized in thatthioamides of the formula (VII) are reacted with ketene acid halides ofthe formula (VI) in the presence of a diluent and, if appropriate, inthe presence of an acid acceptor.

Suitable diluents for the process variant E) according to the inventionare all inert organic solvents. Preference is given to usinghydrocarbons, such as toluene and xylene, furthermore ethers, such asdibutyl ether, glycol dimethyl ether and diglycol dimethyl ether,moreover polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methyl-pyrrolidone.

Suitable acid acceptors for carrying out the process (E) according tothe invention are all customary acid acceptors.

Preference is given to using tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU),diazabicyclononene (DBN), Hünig base and N,N-dimethyl-aniline.

When carrying out the process (E) according to the invention, thereaction temperatures can be varied within a relatively wide range.Advantageously, the reaction is carried out at temperatures between 0°C. and 250° C., preferably between 20° C. and 220° C.

The process (E) according to the invention is advantageously carried outunder atmospheric pressure.

When carrying out the process (E) according to the invention, thereaction components of the formulae (VII) and (VI) in which A, W, X, Yand Z are each as defined above and Hal represents halogen, and, ifappropriate, the acid acceptors, are generally employed in approximatelyequimolar amounts. However, it is also possible to use a relativelylarge excess (up to 5 mol) of one component or the other.

The process (F) is characterized in that compounds of the formula (VIII)in which A, B, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above aresubjected to an intramolecular condensation in the presence of a base.

Suitable diluents for the process (F) according to the invention are allorganic solvents which are inert towards the reaction participants.Preference is given to using hydrocarbons, such as toluene and xylene,furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane,glycol dimethyl ether and diglycol dimethyl ether, moreover polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide andN-methyl-pyrrolidone. It is furthermore possible to use alcohols, suchas methanol, ethanol, propanol, iso-propanol, butanol, isobutanol,tert-butanol.

Suitable bases (deprotonating agents) for carrying out the process (F)according to the invention are all customary proton acceptors.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be employed in thepresence of phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium orpotassium can also be used. Furthermore, alkali metal and alkaline earthmetal amides and hydrides, such as sodium amide, sodium hydride andcalcium hydride, and additionally also alkali metal alkoxides, such assodium methoxide, sodium ethoxide and potassium tert-butoxide can beemployed.

When carrying the process (F) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the reaction is carned out at temperatures between −75° C. and 250° C.,preferably between −50° C. and 150° C. The process (F) according to theinvention is generally carned out under atmospheric pressure.

When carrying out the process (F) according to the invention, thereaction components of the formula (VIII) and the deprotonating basesare generally employed in approximately equimolar amounts. However, itis also possible to use a relatively large excess (up to 3 mol) of onecomponent or the other.

The process (G) is characterized in that compounds of the formula (IX)in which A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y, Z and R⁸ are each as definedabove are subjected to an intramolecular condensation in the presence ofbases.

Suitable diluents for the process (G) according to the invention are allorganic solvents which are inert towards the reaction participants.Preference is given to using hydrocarbons, such as toluene and xylene,furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane,glycol dimethyl ether and diglycol dimethyl ether, moreover polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide andN-methyl-pyrrolidone. Alcohols, such as methanol, ethanol, propanol,iso-propanol, butanol, isobutanol and tert-butanol can also be used.

Suitable bases (deprotonating agents) for carrying out the process (H)according to the invention are all customary proton acceptors.

Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be employed in thepresence of phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(methyltrialkyl(C₉-C₁₀)ammonium chloride) or TDA 1(tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium andpotassium can also be used. Furthermore, alkali metal and alkaline earthmetal amides and hydrides, such as sodium amide, sodium hydride andcalcium hydride, and additionally also alkali metal alkoxides, such assodium methoxide, sodium ethoxide and potassium tert-butoxide can beemployed.

When carrying the process (G) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

The process (G) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (G) according to the invention, thereaction components of the formula (IX) and the deprotonating bases aregenerally employed in approximately equimolar amounts. However, it isalso possible to use a relatively large excess (up to 3 mol) of onecomponent or the other.

For carrying out the process (H) according to the invention,palladium(0) complexes are suitable as catalysts. Preference is givento, for example, tetrakis-(triphenylphosphine)palladium orbis-(triphenylphosphine)-palladium dichloride/triphenyl phosphine.

Suitable acid acceptors for carrying out the process (H) according tothe invention are inorganic or organic bases. These preferably includealkaline earth metal or alkali metal hydroxides, acetates, carbonates orbicarbonates, such as, for example, sodium hydroxide, potassiumhydroxide, barium hydroxide or ammonium hydroxide, sodium acetate,potassium acetate, calcium acetate or ammonium acetate, sodiumcarbonate, potassium carbonate or ammonium carbonate, sodium bicarbonateor potassium bicarbonate, alkali metal fluorides, such as, for example,caesium fluoride, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out the process (H) according to theinvention are water, organic solvents and any mixtures thereof. Examplesinclude: aliphatic, alicyclic or aromatic hydrocarbons, such as, forexample, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; halogenatedhydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,methylene chloride, chloroform, carbon tetrachloride, dichloroethane,trichloroethane or tetrachloroethylene; ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyleneglycol dimethyl ether or anisole; alcohols, such as methanol, ethanol,n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol,propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycolmonomethyl ether, diethylene glycol monomethyl ether; water.

The reaction temperature in the process (H) according to the inventioncan be varied within a relatively wide range. In general, the reactionis carried out at temperatures between 0° C. and +140° C., preferablybetween 50° C. and +100° C.

When carrying out the process (H) according to the invention, thecoupling agents of the formula (X-aI) or (X-b) and compounds of theformulae (I-1′-a) to (I-8′-a) are employed in a molar ratio of from 1:1to 5:1. preferably from 1:1 to 2:1. In general, 0.005 to 0.5 mol,preferably 0.01 mol to 0.1 mol of catalyst is employed per mole of thecompounds of the formulae (I-1′-a) to (I-8′-a). The base is usuallyemployed in excess.

The process (I-α) is characterized in that compounds of the formulae(I-1-a) to (I-7-a) are in each case reacted with carbonyl halides of theformula (XI), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid binder.

Suitable diluents for the process (I-α) according to the invention areall solvents which are inert towards the acid halides. Preference isgiven to using hydrocarbons, such as benzine, benzene, toluene, xyleneand tetralin, furthermore halogenated hydrocarbons, such as methylenechloride, chloroform, carbon tetrachloride, chlorobenzene ando-dichlorobenzene, moreover ketones, such as acetone and methylisopropyl ketone, furthermore ethers, such as diethyl ether,tetrahydrofuran and dioxane, additionally carboxylic esters, such asethyl acetate, and also strongly polar solvents, such as dimethylsulphoxide and sulpholane. The hydrolytic stability of the acid halidepermitting, the reaction can also be carried out in the presence ofwater.

Suitable acid binders for the reaction according to the process (I-α)according to the invention are all customary acid acceptors. Preferenceis given to using tertiary amines, such as triethylamine, pyridine,diazabicyclooctane (DABCO), diazabicyclo-undecene (DBU),diazabicyclononene (DBN), Hünig base and N,N-dimethyl-aniline,furthermore alkaline earth metal oxides, such as magnesium oxide andcalcium oxide, moreover alkali metal and alkaline earth metalcarbonates, such as sodium carbonate, potassium carbonate and calciumcarbonate, and also alkali metal hydroxides such as sodium hydroxide andpotassium hydroxide.

The reaction temperatures in the process (I-α) according to theinvention can be varied within a relatively wide range. In general, thereaction is carried out at temperatures between −20° C. and +150° C.,preferably between 0° C. and 100° C.

When carrying out the process (I-α) according to the invention, thestarting materials of the formulae (I-1-a) to (I-7-a) and the carbonylhalide of the formula (XI) are generally in each case employed inapproximately equivalent amounts. However, it is also possible to employa relatively large excess (up to 5 mol) of the carbonyl halide. Work-upis carried out by customary methods.

The process (I-8) is characterized in that compounds of the formulae(I-1-a) to (I-7-a) are reacted with carboxylic anhydrides of the formula(XII), if appropriate in the presence of a diluent and if appropriate inthe presence of an acid binder.

Preferred diluents for the process (I-β) according to the invention arethose diluents which are also preferred when acid halides are used.Otherwise, it is also possible for a carboxylic anhydride employed inexcess to act simultaneously as a diluent.

In the process (I-β), acid binders which are added, if appropriate, arepreferably those acid binders which are also preferred when acid halidesare used.

In the process (I-β) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between −20° C. and +150°C., preferably between 0° C. and 100° C.

When carrying out the process (I-β) according to the invention, thestarting materials of the formulae (I-1-a) to (I-7-a) and the carboxylicanhydride of the formula (XII) are generally each employed inapproximately equivalent amounts. However, it is also possible to use arelatively large excess (up to 5 mol) of the carboxylic anhydride.Work-up is carried out by customary methods.

In general, the adopted procedure is to remove diluent and excesscarboxylic anhydride and also the carboxylic acid formed by distillationor by washing with an organic solvent or with water.

The process (J) is characterized in that compounds of the formulae(I-1-a) to (I-7-a) are in each case reacted with chloroformic esters orchloroformic thiol esters of the formula (XV), if appropriate in thepresence of a diluent and if appropriate in the presence of an acidbinder.

Suitable diluents for the reaction according to the process (J)according to the invention are all customary acid acceptors. Preferenceis given to using tertiary amines, such as triethylamine, pyridine,DABCO, DBU, DBA, Hünig base and N,N-dimethyl-aniline, furthermorealkaline earth metal oxides, such as magnesium oxide and calcium oxide,moreover alkali metal carbonates and alkaline earth metal carbonates,such as sodium carbonate, potassium carbonate and calcium carbonate, andalso alkali metal hydroxides such as sodium hydroxide and potassiumhydroxide.

Suitable diluents for the process (J) according to the invention are allsolvents which are inert towards the chloroformic esters or chloroformicthiol esters. Preference is given to using hydrocarbons, such asbenzine, benzene, toluene, xylene and tetralin, furthermore halogenatedhydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones,such as acetone and methyl isopropyl ketone, furthermore ethers, such asdiethyl ether, tetrahydrofuran and dioxane, additionally carboxylicesters, such as ethyl acetate, and also strongly polar solvents, such asdimethyl sulphoxide and sulpholane.

When carrying out the process (J) according to the invention thereaction temperatures can be varied within a relatively wide range. Ifthe reaction is carried out in the presence of a diluent and an acidbinder, the reaction temperatures are generally between −20° C. and+100° C., preferably between 0° C. and 50° C.

The process (J) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (J) according to the invention, thestarting materials of the formulae (I-1-a) to (I-7-a) and theappropriate chloroformic ester or chloroformic thiol ester of theformula (XIII) are generally in each case employed in approximatelyequivalent amounts. However, it is also possible to employ a relativelylarge excess (up to 2 mol) of one component or the other. Work-up iscarried out by customary methods. In general, precipitated salts areremoved and the reaction mixture that remains is concentrated bystripping the diluent.

The process (K) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-7-a) are in each case reactedwith compounds of the formula (XIV) in the presence of a diluent and, ifappropriate, in the presence of an acid binder.

In the preparation process (K), approximately 1 mol ofchloromonothioformic ester or chlorodithioformic ester of the formula(XIV) is reacted per mole of starting material of the formulae (I-1-a)to (I-7-a), at from 0 to 120° C., preferably from 20 to 60° C.

Suitable diluents which are added if appropriate are all inert polarorganic solvents, such as ethers, amides, sulphones, sulphoxides, butalso halogenoalkanes.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethyl-formamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-7-a) is prepared by addition of strong deprotonating agents, suchas, for example, sodium hydride or potassium tert-butoxide, it is notnecessary to add further acid binders.

If acid binders are employed, these are customary inorganic or organicbases, for example sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine, triethylamine.

The reaction can be carried out at atmospheric pressure or underelevated pressure and is preferably carried out at atmospheric pressure.Work-up is carried out by customary methods.

The process (L) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-7-a) are in each case reactedwith sulphonyl chlorides of the formula (XV), if appropriate in thepresence of a diluent and if appropriate in the presence of an acidbinder.

In the preparation process (L), approximately 1 mol of sulphonylchloride of the formula (XV) is reacted per mole of starting material ofthe formula (I-1-a to I-7-a), at from −20 to 150° C., preferably at from20 to 70° C.

Suitable diluents which are added if appropriate are all inert polarorganic solvents, such as ethers, amides, nitriles, sulphones,sulphoxides or halogenated hydrocarbons, such as methylene chloride.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethyl-formamide and methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-7-a) is prepared by addition of strong deprotonating agents (suchas, for example, sodium hydride or potassium tert-butoxide), it is notnecessary to add further acid binders.

If acid binders are employed, these are customary inorganic or organicbases, for example sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine, triethylamine.

The reaction can be carried out at atmospheric pressure or underelevated pressure and is preferably carried out at atmospheric pressure.Work-up is carried out by customary methods.

The process (M) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-7-a) are in each case reactedwith phosphorus compounds of the formula (XVI), if appropriate in thepresence of a diluent and if appropriate in the presence of an acidbinder.

In the preparation process (M), 1 to 2, preferably 1 to 1.3, mol of thephosphorus compound of the formula (XVI) are reacted per mole of thecompounds (I-1-a) to (I-7-a) at temperatures between −40° C. and 150°C., preferably between −10 and 110° C., to give compounds of theformulae (I-1-e) to (I-7-e).

Suitable solvents which are added if appropriate are all inert polarorganic solvents, such as ethers, amides, nitriles, alcohols, sulphides,sulphones, sulphoxides, etc.

Preference is given to using acetonitrile, dimethyl sulphoxide,tetrahydrofuran, dimethylformamide, methylene chloride.

Suitable acid binders which are added if appropriate are customaryinorganic or organic bases such as hydroxides, carbonates or amines.Examples include sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine, triethylamine.

The reaction can be carried out at atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out by customary methods of organicchemistry. The resulting end products are preferably purified bycrystallization, chromatographic purification or by so-called “incipientdistillation”, i.e. removal of the volatile components under reducedpressure.

The process (N) is characterized in that compounds of the formulae(I-1-a) to (I-7-a) are reacted with metal hydroxides or metal alkoxidesof the formula (XVII) or amines of the formula (XVIII), if appropriatein the presence of a diluent.

Preferred diluents for the process (N) according to the invention areethers, such as tetrahydrofuran, dioxane, diethyl ether, or elsealcohols, such as methanol, ethanol, isopropanol, but also water.

The process (N) according to the invention is generally carried outunder atmospheric pressure.

The reaction temperatures are generally between −20° C. and 100° C.,preferably between 0° C. and 50° C.

The process (O) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-7-a) are in each case reactedwith (O-α) compounds of the formula (XIX), if appropriate in thepresence of a diluent and if appropriate in the presence of a catalyst,or (O-β) with compounds of the formula (XX), if appropriate in thepresence of a diluent and if appropriate in the presence of an acidbinder.

In the preparation process (O-α), approximately 1 mol of isocyanate ofthe formula (XIX) is reacted per mole of starting material of theformulae (I-1-a) to (I-7-a), at from 0 to 100° C., preferably at from 20to 50° C.

Suitable diluents which are added if appropriate are all inert organicsolvents, such as ethers, amides, nitriles, sulphones and sulphoxides.

If appropriate, catalysts may be added to accelerate the reaction. Veryadvantageously, the catalysts which are employed are organotincompounds, such as, for example, dibutyltin dilaurate. The reaction ispreferably carried out at atmospheric pressure.

In the preparation process (O-β), approximately 1 mol of carbamoylchloride of the formula (XX) is reacted per mole of starting material ofthe formulae (I-1-a) to (I-7-a), at from −20 to 150° C., preferably atfrom 0 to 70° C.

Suitable diluents which are added if appropriate are all inert polarorganic solvents, such as ethers, amides, sulphones, sulphoxides orhalogenated hydrocarbons.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethyl-formamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-7-a) is prepared by addition of strong deprotonating agents (suchas, for example, sodium hydride or potassium tert-butoxide), it is notnecessary to add further acid binders.

If acid binders are employed, these are customary inorganic or organicbases, for example sodium hydroxide, sodium carbonate, potassiumcarbonate, triethylamine or pyridine.

The reaction can be carried out at atmospheric pressure or underelevated pressure and is preferably carried out at atmospheric pressure.Work-up is carried out by customary methods.

The active compounds having good plant tolerance and favourablewarm-blood toxicity are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene sector. They are preferably used as cropprotection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. andSchistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp. andDamalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi and Frankliniella occidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematoden include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

At certain concentrations or application rates, the compounds accordingto the invention may, if appropriate, also be used as herbicides andmicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they may also be used as intermediates or precursors forthe synthesis of further active compounds.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

As solid carriers there are suitable:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly disperse silica,alumina and silicates; as solid carriers for granules there aresuitable: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, and also syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks;as emulsifiers and/or foam-formers there are suitable: for examplenonionic and anionic emulsifiers, such as polyoxyethylene fatty acidesters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonatesand also protein hydrolysates; as dispersants there are suitable: forexample lignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphoric acid esters, carbamates,carboxylates, chlorinated hydrocarbons, phenylureas and substancesproduced by microorganisms, inter alia.

Particularly favourable examples of co-components in mixtures are thefollowing compounds:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, capsimycin, captafol, captan, carbendazim,    carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,    chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,    cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,-   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,    fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover,    fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazole-cis, furmecyclox,-   guazatine,-   hexachlorobenzene, hexaconazole, hymexazole,-   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,    iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),    iprodione, irumamycin, isoprothiolane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,    metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,-   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,    oxyfenthiin,-   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,    pimancin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,    procymidone, propamocarb, propanosine-sodium, propiconazole,    propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,    pyroxyfur,-   quinconazole, quintozene (PCNB),-   sulphur and sulphur preparations,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,    triazbutil, triazoxide, trichlamide, tricyclazole,-   tridemorph, triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G,-   OK-8705,-   OK-8801,-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-3-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, isopropyl    {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,-   ethyl[(4-chlorophenyl)-azo]-cyanoacetate,-   potassium hydrogen carbonate,-   methanetetrathiol sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,    methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide.-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulfonamide,-   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(4-hex ylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine-sodium salt,-   O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,    Bactericides:-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.    Insecticides/Acaricides/Nematicides:-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin,    AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus    subtilis, Bacillus thuringiensis, Baculoviridae, Beauveria bassiana,    Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate,    betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin,    bio-permethrin, BPMC, bromophos A, bufencarb, buprofezin,    butathiofos, butocarboxim, butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosuifan,    cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,    chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,    chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin,    cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin,    cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,-   deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,    diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos,    diofenolan, disulfoton, docusat-sodium, dofenapyn,-   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,    esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox,    etoxazole, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide,    fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin,    fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil,    fluazinam, fluazuron, flubrocythrinate, flucycloxuron,    flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos,    fosmethilan, fosthiazate, fubfenprox, furathiocarb,-   granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, metharhizium    anisopliae, metharhizium flavoviride, methidathion, methiocarb,    methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,    milbemectin, monocrotophos,-   naled, nitenpyram, nithiazine, novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,    propoxur, prothiofos, prothoate, pymetrozine, pyraclofos,    pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,    pyriproxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron. tefluthrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, thetacypermethnn, thiamethoxam, thiapronil,    thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,    thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,    triazophos, triazurone, trichlophenidine, trichiorfon, triflumuron,    trimethacarb, vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302,-   zeta-cypermethrin, zolaprofos,-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropalecarboxylate,-   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamnate.-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4,5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,    dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,-   ethyl[2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compounds according to the invention can furthermore bepresent when used as insecticides in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds, without it beingnecessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds according to the invention are also suitable forcontrolling arthropods which infest agricultural productive livestock,such as, for example, cattle, sheep, goats, horses, pigs, donkeys,camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees,other pets, such as, for example, dogs, cats, caged birds and aquariumfish, and also so-called test animals, such as, for example, hamsters,guinea pigs, rats and mice. By controlling these arthropods, cases ofdeath and reduction in productivity (for meat, milk, wool, hides, eggs,honey etc.) should be diminished, so that more economic and easieranimal husbandry is possible by use of the active compounds according tothe invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injection(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundscan be used as formulations (for example powders, emulsions,free-flowing compositions), which comprise the active compounds in anamount of 1 to 80% by weight, directly or after 100 to 10 000-folddilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention also have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as beingpreferred—but without any limitation:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobiusmollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctusplanicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale,Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus,Bostrychus capucins, Heterobostrychus brunneus and Sinoxylon spec.Dinoderus minutus.

Hymenopterons, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerusaugur

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotcrmes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus.

Bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and wood processed wood products which can be protected by theagents according to the invention or mixtures comprising these are to beunderstood as meaning, for example: building timber, wooden beams,railway sleepers, bridge components, boat jetties, wooden vehicles,boxes, pallets, containers, telegraph poles, wood panelling, woodenwindows and doors, plywood, chipboard, joinery or wooden products whichare used quite generally in house-building or in building joinery.

The active compounds can be used as such, in the form of concentrates orin generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyestuffs and pigments, and also other processingauxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compound,based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., terpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin,silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamcthrin, permcethrin, imidacloprid,NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid,methoxyphenoxide and triflumuron, and also fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with saltwateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis-(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

algicides such as

2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,dichlorophen, diuron, endothal, fentine acetate, isoproturon,methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

fungicides such as

benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,dichlofluanid, fluor-folpet, 3-iodo-2-propinyl butylcarbamate,tolylfluanid and azoles such as

azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole,propiconazole and tebuconazole;

molluscicides such as

fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb andtrimethacarb;

or conventional antifouling active compounds such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulphone, 2-(N,N-di-methylthiocarbamoylthio)-5-nitrothiazyl, potassium,copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridine-triphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetra-methylthiuram disulphide and2,4,6-trichlorophenylmaleiimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaces such as, for example, dwellings, factory halls, offices, vehiclecabins and the like. They can be employed in domestic insecticideproducts for controlling these pests alone or in combination with otheractive compounds and auxiliaries. They are active against sensitive andresistant species and against all developmental stages. These pestsinclude:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Onlscus asellus, Porcellioscaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomcstica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.

They are used in the household insecticides sector alone or incombination with other suitable active compounds such as phosphoricesters, carbamates, pyrethroids, growth regulators or active compoundsfrom other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The active compounds according to the invention can be used asdefoliants, desiccants, haulm killers and, especially, as weed killers.Weeds in the broadest sense are understood to mean all plants which growin locations where they are undesired.

Whether the substances according to the invention act as total orselective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledonous Weeds of the Genera:

Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex,Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium,Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia,Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium,Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis,Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus,Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida,Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi,Trifolium, Urtica, Veronica, Viola, Xanthium.

Dicotyledonous Crops of the Genera:

Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus,Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana,Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous Weeds of the Genera:

Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria,Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium,Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa,Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa,Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa,Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Monocotyledonous Crops of the Genera:

Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum,Secale, Sorghum, Triticale, Triticum, Zea.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The active compounds according to the invention are suitable, dependingon the concentration, for the total control of weeds, for example onindustrial terrain and rail tracks, and on paths and areas with andwithout tree plantings. Similarly, the active compounds according to theinvention can be employed for controlling weeds in perennial crops, forexample forests, decorative tree plantings, orchards, vineyards, citrusgroves, nut orchards, banana plantations, coffee plantations, teaplantations, rubber plantations, oil palm plantations, cocoaplantations, soft fruit plantings and hop fields, on lawns, turf andpastureland, and for the selective control of weeds in annual crops.

The compounds according to the invention have strong herbicidal activityand a broad activity spectrum when used on the soil or on above-groundparts of plants. To a certain extent, they are also suitable for theselective control of monocotyledonous and dicotyledonous weeds inmonocotyledonous and dicotyledonous crops, both by the pre-emergence andby the post-emergence method.

At certain concentrations or application rates, the active compoundsaccording to the invention can also be employed for controlling animalpests and fungal or bacterial plant diseases. If appropriate, they canalso be used as intermediates or precursors for the synthesis of otheractive compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, inclusive of the transgenicplants and inclusive of the plant varieties protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodto mean all above-ground and underground parts and organs of plants,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seed, also byapplying one or more coats.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant varieties, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant varieties obtained by genetical engineering, ifappropriate in combination with conventional methods (Genetic ModifiedOrganisms), and parts thereof are treated. The term “parts” or “parts ofplants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant varieties which are in eachcase commercially available or in use are treated according to theinvention.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The transgenic plants or plant varieties (i.e. those obtained bygenetical engineering) which are preferred according to the inventioninclude all plants which, in the genetic modification, received geneticmaterial which imparted particularly advantageous useful properties(“traits”) to these plants. Examples of such properties are better plantgrowth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, better quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products. Further and particularly emphasized examples ofsuch properties are a better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape andalso fruit plants (with the fruits apples, pears, citrus fruits andgrapevines), and particular emphasis is given to maize, soya beans,potatoes, cotton and oilseed rape. Traits that are emphasized are inparticular increased defence of the plants against insects by toxinsformed in the plants, in particular those formed by the genetic materialfrom Bacillus thuringiensis (for example by the genes CryIA(a),CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb andCryIF and also combinations thereof) (hereinbelow referred to as “Btplants”). Traits that are furthermore particularly emphasized are theincreased tolerance of the plants to certain herbicidally activecompounds, for example imidazolinones, sulphonylureas, glyphosate orphosphinotricin (for example the “PAT” gene). The genes which impart thedesired traits in question can also be present in combination with oneanother in the transgenic plants. Examples of “Bt plants” which may bementioned are maize varieties, cotton varieties, soya bean varieties andpotato varieties which are sold under the trade names YIELD GARD® (forexample maize, cotton, soya beans), KnockOut® (for example maize),StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) andNewLeaf® (potato). Examples of herbicide-tolerant plants which may bementioned are maize varieties, cotton varieties and soya bean varietieswhich are sold under the trade names Roundup Ready® (tolerance toglyphosate, for example maize, cotton, soya bean), Liberty Link®(tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, forexample maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize). Of course, these statements also apply to plant varieties havingthese or still to be developed genetic traits, which plants will bedeveloped and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the active compound mixturesaccording to the invention. The preferred ranges stated above for theactive compounds also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the mixturesspecifically mentioned in the present text.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspo-emulsion concentrates,natural and synthetic substances impregnated with active compound, andmicroencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is to say liquid solventsand/or solid carriers, optionally with the use of surfactants, that isto say emulsifiers and/or dispersants and/or foam formers.

If the extender used is water, it is also possible to use, for example,organic solvents as auxiliary solvents. Liquid solvents which are mainlysuitable are: aromatics, such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols, such as butanol orglycol, and also their ethers, ketones, such as acetone, methyl ethylketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents, such as dimethylformamide and dimethyl sulphoxide, and water.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth; and ground syntheticminerals, such as finely divided silica, alumina and silicates; suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks, such as calcite, marble, pumice, sepiolite, dolomite andsynthetic granules of inorganic and organic meals, and granules oforganic material, such as sawdust, coconut shells, maize cobs andtobacco stalks; suitable emulsifiers and/or foam formers are: forexample nonionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonatesand protein hydrolysates; suitable dispersants are: for examplelignosulphite waste liquors and methylcellulose.

Tackifiers, such as carboxymethylcellulose, natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, and also naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants, such as inorganic pigments, for exampleiron oxide, titanium oxide, Prussian blue, and organic dyestuffs, suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients, such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in their formulations, can also be used as mixtures withknown herbicides and/or substances which improve the compatibility withcrop plants (“safeners”), finished formulations or tank mixes beingpossible. Also possible are mixtures with weed-killers comprising one ormore known herbicides and a safener.

Possible components for the mixtures are known herbicides, for example

acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos,asulam, atrazine, aza-fenidin, azimsulfuron, BAS-662H, beflubutamid,benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazon,benzfendizone, benzobicyclon, benzofenap, benzoylprop (-ethyl),bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromo-fenoxim,bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate,cafen-strole, caloxydim, carbetamide, carfentrazone (-ethyl),chlomethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl),chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl),cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne,cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D,2,4-DB, desmedipham, diallate, dicamba, dichlorprop (—P), diclofop(-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican,diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn,dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr,diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin,ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxy-sulfuron,etobenzanid, fenoxaprop (—P-ethyl), fentrazamide, flamprop (-isopropyl,-isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (—P-butyl),fluazolate, flu-carbazone (-sodium), flufenacet, flumetsulam,flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam,fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam,flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl),fluridone, fluoroxypyr (-butoxypropyl, -meptyl), flurprimidol,flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron,glufosinate (-ammonium), gly-phosate (-isopropylammonium), halosafen,haloxyfop (-ethoxyethyl, —P-methyl), hex-azinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil,isopropalin, isoproturon, isouron, isoxaben, isoxachlortole,isoxaflutole, isoxapyri-fop, lactofen, lenacil, linuron, MCPA, mecoprop,mefenacet, mesotrione, meta-mitron, metazachlor, methabenzthiazuron,metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron,metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide,napropamide, neburon, nicosulfuron, norflurazon, orben-carb, oryzalin,oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen,paraquat, pelargonsaiure, pendimethalin, pendralin, pentoxazone,phenmedipham, picolinafen, piperophos, pretilachlor, primisulfuron(-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop,propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb,prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol,pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac,quinmerac, quinoclamine, quizalofop (-p-ethyl, -p-tefuryl), rimsulfuron,sethoxydim, simazine, simetryn, sulcotnone, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim,terbuthylazine, terbutryn, thenylchlor, thiaflu-amide, thiazopyr,thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil,tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr,tridiphane, tri-fluralin, trifloxysulfuron, triflusulfuron (-methyl),tritosulfuron.

A mixture with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of theformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in a customary manner, for example bywatering, spraying, atomizing, or broadcasting.

The active compounds according to the invention can be applied bothbefore and after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a relatively widerange. It depends essentially on the nature of the desired effect. Ingeneral, the amounts used are between 1 g and 10 kg of active compoundper hectare of soil surface, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to theinvention is illustrated by the examples below.

PREPARATION EXAMPLES Example I-1-a-1

At 60° C., 7.4 g of the compound of Example II-1, dissolved in 1 ml ofanhydrous dimethylformamide (DMF), are added dropwise to 6.5 g ofpotassium tert-butoxide in 25 ml of anhydrous DMF, and stirring iscontinued and the reaction is monitored by thin-layer chromatography.After the reaction has ended, 170 ml of ice-water are added, the mixtureis, at from 0° C. to 10° C., acidified with conc. hydrochloric acid topH 2 and filtered off with suction, and the filter cake is washed withice-water. The residue is purified chromatographically on silica gelusing the mobile phase methylene chloride/methanol 9:1.

Yield: 3.90 g (

58.00% of theory), m.p. 199° C.

The following compounds of the formula (I-a-1) were obtained similarlyto Example (I-1-a-1) and in accordance with the general preparationinstructions

(I-a-1)

Ex. No. W X Y Z A B m.p. ° C. Isomer I-1-a-2 CH₃ C₂H₅ C₂H₅ H—(CH₂)₂—CHCH₃—(CH₂)₂— 154 β I-1-a-3 CH₃ C₂H₅ C₂H₅ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 225 β I-1-a-4 C₂H₅ C₂H₅ C₂H₅ H CH₃ CH₃ 200 —I-1-a-5 C₂H₅ C₂H₅ C₂H₅ H —(CH₂)₂—CHCH₃—(CH₂)₂— 115 β I-1-a-6 C₂H₅ C₂H₅C₂H₅ H —(CH₂)₂—CHOCH₃—(CH₂)₂— 222 β I-1-a-7 i-C₃H₇ i-C₃H₇ i-C₃H₇ H—(CH₂)₂—CHOCH₃—(CH₂)₂— >230 β I-1-a-8 CH₃ C₂H₅ CH₃ H CH₃ CH₃ >220 —I-1-a-9 CH₃ C₂H₅ CH₃ H —(CH₂)₂—CHCH₃—(CH₂)₂— 114 β I-1-a-10 C₂H₅ C₂H₅ HH —(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-11 C₂H₅ C₂H₅ H H—(CH₂)₂—O—(CH₂)₂— >220 — I-1-a-12 CH₃ C₂H₅ H H CH₃ CH₃ 109 — I-1-a-13CH₃ C₂H₅ H H —(CH₂)₂—CHCH₃—(CH₂)₂— 216 β I-1-a-14 H CH₃ H i-C₄H₉ CH₃ CH₃160 — I-1-a-15 H CH₃ H C₃H₇ —(CH₂)₂—CHOCH₃—(CH₂)₂— 197 β I-1-a-16 H CH₃H C₃H₇ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— 193 β I-1-a-17 H CH₃ H i-C₄H₉—(CH₂)₂—CHOCH₃—(CH₂)₂— 233 β I-1-a-18 H CH₃ H i-C₄H₉—(CH₂)₂—CHOC₂H₅—(CH₂)₂— 184 β I-1-a-19 H CH₃ CH₃ C₂H₅—(CH₂)₂—CHOCH₃—(CH₂)₂— 156 β I-1-a-20 H CH₃ CH₃ C₂H₅—(CH₂)₂—CHOC₂H₅—(CH₂)₂— 168 β I-1-a-21 CH₃ CH₃ —C≡CH H—(CH₂)₂—CHOCH₃—(CH₂)₂— 127 β I-1-a-22 H CH₃ C₂H₅ H —(CH₂)₂—CHCH₃—(CH₂)₂—211 β I-1-a-23 H C₂H₅ CH₃ H —(CH₂)₂—CHCH₃—(CH₂)₂— 210 β I-1-a-24 H C₂H₅CH₃ H —(CH₂)₂—O—(CH₂)₂— >220 — I-1-a-25 H C₂H₅ CH₃ H CH₃ CH₃ 192 —I-1-a-26 H CH₃ H C₂H₅ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— 181 β I-1-a-27 H CH₃ HC₂H₅ —(CH₂)₂—CHOCH₃—(CH₂)₂— 222 β I-1-a-28 CH₃ CH₃ CH═CH₂ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 278 β I-1-a-29 CH₃ CH₃ C₂H₅ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 268 β I-1-a-30 CH₃ CH₃ C₂H₅ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 248 α

Example I-1-b-1

2.5 g of the compound I-1-a-10 in 50 ml of anhydrous ethyl acetate areheated at reflux with 1.7 ml of triethylamine, 1.3 ml of isobutyrylchloride in 5 ml of anhydrous ethyl acetate are added dropwise, themixture is stirred at reflux and the reaction is monitored by thin-layerchromatography. The solvent is distilled off and the residue is taken upin methylene chloride, washed with 50 ml of 0.5 N NaOH, dried andconcentrated using a rotary evaporator. The residue is thenrecrystallized from methyl tert-butyl ether (MTB ether)/n-hexane.

Yield: 2 g (

65% of theory), m.p. 209° C.

The following compounds of the formula (I-1-b) are obtained similarly toExamples (I-1-b-1) and in accordance with the general preparationinstructions

(I-1-b)

Ex. No. W X Y Z A B R¹ m.p. ° C. Isomer I-1-b-2 CH₃ C₂H₅ H H CH₃ CH₃i-C₃H₇ 145 — I-1-b-3 CH₃ C₂H₅ H H —(CH₂)₂—CHCH₃—(CH₂)₂— H₅C₂—O—CH₂— 135β I-1-b-4 CH₃ C₂H₅ H H CH₃ CH₃ H₅C₂—O—CH₂— 76 — I-1-b-5 H CH₃ C₂H₅ H—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 201 β I-1-b-6 H CH₃ C₂H₅ H—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₄H₉ 215 β I-1-b-7 H C₂H₅ CH₃ H—(CH₂)₂—O—(CH₂)₂— i-C₃H₇ 190 —

Example I-1-c-1

2.51 g of the compound of the formula I-1-a-10 and 1.2 ml oftriethylamine are initially charged. At from 0 to 10° C., 0.8 ml ofethyl chloroformate in 5 ml of anhydrous dichloromethane are addeddropwise, the mixture is stirred at room temperature and the reaction ismonitored by thin-layer chromatography. The mixture is then washed with0.5 N NaOH and dried, and the solvent is distilled off. The residue isrecrystallized from methyl tert-butyl ether/n-hexane.

Yield: 1.1 g (

30% of theory), m.p. 178° C.

The following compounds of the formula (I-1-c) are obtained similarly toExample (I-1-c-1) and in accordance with the general preparationinstructions

(I-1-c)

Ex. No. W X Y Z A B M R² m.p. ° C. Isomer I-1-c-2 C₂H₅ C₂H₅ H H—(CH₂)₂—O—(CH₂)₂— O C₂H₅ 194 β I-1-c-3 CH₃ C₂H₅ H H CH₃ CH₃ O C₂H₅ 119 —I-1-c-4 CH₃ CH₃ —C≡CH H —(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ 171 β I-1-c-5 HCH₃ C₂H₅ H —(CH₂)₂—CHCH₃—(CH₂)₂— O i-C₄H₉ 155 β I-1-c-6 H C₂H₅ CH₃ H—(CH₂)₂—O—(CH₂)₂— O C₂H₅ 215 — I-1-c-7 H CH₃ CH₃ C₂H₅—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ 137 β I-1-c-8 H CH₃ CH₃ C₂H₅—(CH₂)₂—CHOC₂H₅—(CH₂)₂— O C₂H₅ 168 β

Example II-1

Example II-1

At 80° C., 7.5 g of 2,4-diethyl-6-methyl-phenylacetic acid and 9.2 ml ofthionyl chloride are stirred until evolution of gas has ceased. Excessthionyl chloride is distilled off and the residue is taken up in 30 mlof dry THF. At from 0 to 10° C., this solution is added dropwise to 12.3g of methyl 2-amino-2-methylpropanoate in 320 ml of dry THF admixed with24.6 ml of triethylamine, and the mixture is stirred at room temperaturefor 1 h. This solution is then concentrated using a rotary evaporator,the residue is taken up in methylene chloride and 1 N HCl, the productis extracted and the organic phase is dried and concentrated using arotary evaporator. The residue is recrystallized from MTBether/n-hexane.

Yield: 8.07 g (

66% of theory), m.p. 120-122° C.

Example II-11

At an internal temperature of from 30 bis 40° C., 10.3 g of the compoundof Example XXVII-1, as a suspension in 110 ml of methylene chloride, areadded to 16.9 g of conc. sulphuric acid, and the mixture is stirred for2 h. 23 ml of dry methanol are added dropwise, and the mixture isstirred at from 40 to 70° C. for 6 h. The solution is poured onto 0.18kg of ice, the product is extracted with methylene chloride and theorganic phase is washed with an NaHCO₃ solution. The organic phase isdried and concentrated using a rotary evaporator, and the residue isrecrystallized from MTB ether/n-hexane.

Yield: 8.7 g (76% of theory), m.p. 137° C.

The following compounds of the formula (II) are obtained similarly toExample (II-1) and in accordance with the general preparationinstructions

(II)

Ex. No. W X Y Z A B R⁸ m.p. ° C. Isomer II-2 CH₃ C₂H₅ C₂H₅ H—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 169 β II-3 CH₃ C₂H₅ C₂H₅ H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 94 β II-4 C₂H₅ C₂H₅ C₂H₅ H CH₃ CH₃ CH₃ 109 —II-5 C₂H₅ C₂H₅ C₂H₅ H —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 141 β II-6 C₂H₅ C₂H₅C₂H₅ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 165 β II-7 i-C₃H₇ i-C₃H₇ i-C₃H₇ H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 112 β II-8 CH₃ C₂H₅ CH₃ H CH₃ CH₃ CH₃ 126 —II-9 CH₃ C₂H₅ CH₃ H —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 101 β II-10 C₂H₅ C₂H₅ H H—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 108 β II-11 C₂H₅ C₂H₅ H H —(CH₂)₂—O—(CH₂)₂—CH₃ 137 — II-12 CH₃ C₂H₅ H H CH₃ CH₃ CH₃ 102 — II-13 CH₃ C₂H₅ H H—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 169 β II-14 H CH₃ H i-C₄H₉ CH₃ CH₃ CH₃ 93 —II-15 H CH₃ H C₃H₇ —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 112 β II-16 H CH₃ H C₃H₇—(CH₂)₂—CHOC₂H₅—(CH₂)₂— CH₃ 71 β II-17 H CH₃ H i-C₄H₉—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 69 β II-18 H CH₃ H i-C₄H₉—(CH₂)₂—CHOC₂H₅—(CH₂)₂— CH₃ 61 β II-19 H CH₃ CH₃ C₂H₅—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 151 β II-20 H CH₃ CH₃ C₂H₅—(CH₂)₂—CHOC₂H₅—(CH₂)₂— CH₃ 123 β II-21 CH₃ CH₃ —C≡CH H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 141 β II-22 H CH₃ C₂H₅ H—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 98 β II-23 H C₂H₅ CH₃ H —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ 149 β II-24 H C₂H₅ CH₃ H —(CH₂)₂—O—(CH₂)₂— CH₃ 164 — II-25 H C₂H₅CH₃ H CH₃ CH₃ CH₃ 141 — II-26 H CH₃ H C₂H₅ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— CH₃103 β II-27 H CH₃ H C₂H₅ —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ Oil β II-28 CH₃ CH₃CH═CH₂ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 234 β II-29 CH₃ CH₃ C₂H₅ H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 140 β

Example XXVII-1

At 80° C., 7.68 g of 2,4-diethyl-6-methyl-phenylacetic acid and 9.1 mlof thionyl chloride are stirred until evolution of gas has ceased.Excess thionyl chloride is distilled off, and the residue is taken up in40 ml of dry toluene. At from 0 to 10° C., this solution is addeddropwise to 9 g of 4-amino-4-cyano-tetrahydropyran in 80 ml of dry THFadmixed with 6.2 ml of triethylamine, and the mixture is stirred at roomtemperature for 1 h. The solution is then concentrated using a rotaryevaporator, the residue is taken up in 1 N HCl in methylene chloride andthe organic phase is dried and concentrated using a rotary evaporator.The residue is recrystallized from MTB-ether/n-hexane.

Yield: 10.3 g (

85% of theory), m.p. 155° C.

Similarly to Example XXVII-1, Example XXVII-2 with m.p. 142° C. isobtained.

Example I-2-a-1

At from 0 to 10° C., 16.6 g of the compound of Example III-1, dissolvedin 50 ml of anhydrous DMF, are added dropwise to 8.4 g of potassiumtert-butoxide in 50 ml of anhydrous DMF, and the mixture is stirred atroom temperature for 8 h. After the reaction has ended, 1000 ml of 1 NHCl are added dropwise with ice-cooling, and the mixture is stirred for30 min. The precipitate is filtered off, washed with water and driedunder reduced pressure.

Yield: 11.5 g (

80% of theory), m.p. 135° C.

The following compounds of the formula (I-2-a) are obtained similarly toExample (I-2-a-1) and in accordance with the general preparationinstructions

(I-2-a)

Ex. No. W X Y Z A B m.p. ° C. I-2-a-2 C₂H₅ C₂H₅ H H—(CH₂)₂—CHOCH₃—(CH₂)₂— Oil I-2-a-3 CH₃ C₂H₅ CH₃ H —(CH₂)₅— 223-225I-2-a-4 CH₃ C₂H₅ CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— 175-178 I-2-a-5 CH₃ C₂H₅C₂H₅ H —(CH₂)₂—CHOCH₃—(CH₂)₂— Oil

Example I-2-b-1

2.08 ml of triethylamine are added to 2.86 g of the compound of ExampleI-2-a-1 dissolved in 40 ml of dry methylene chloride (CH₂Cl₂). At 0-10°C., 1.5 g of pivaloyl chloride in 10 ml of CH₂Cl₂ are added, and themixture is stirred at room temperature for 20 h.

The reaction solution is washed first with 10% strength citric acid andthen with 1 N NaOH, dried and concentrated using a rotary evaporator,and the residue is stirred with petroleum ether.

Yield: 2.2 g (

60% of theory), m.p. 110-112° C.

Example I-2-b-2

1.2 g (2.76 mmol) of the compound of Example I-2-b-2 from WO 97/02243are initially charged in 20 ml of toluene, 3.5 g (11 mmol) oftributyl-vinyl tin, 133 mg (0.11 mmol) of Pd(PPh₃)₄ and 2 crystals of2,6-di-t-butyl-4-methylcresol are added the mixture is boiled at refluxovernight and then concentrated using a rotary evaporator.

For purification, the crude mixture is chromatographed on silica gel,where first excess tin compounds are eluted with cyclohexane and then,by changing the mobile phase to cyclohexane/ethyl acetate (2:1), theproduct is eluted. Further purification was achieved by triturating thecrude product with petroleum ether.

Yield: 0.46 g (44% of theory) of colourless crystals of m.p. 152-155° C.

The following compounds of the formula (I-2-b) are obtained similarly toExamples (I-2-b-1) and (I-2-b-2) and in accordance with the generalpreparation instructions

(I-2-b)

Ex. No. W X Y Z A B R¹ m.p. ° C. I-2-b-3 H C₂H₅ CH₃ H —(CH₂)₅—t-C₄H₉—CH₂ 162-164 I-2-b-4 C₂H₅ C₂H₅ H H —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉Oil I-2-b-5 CH₃ CH₃ CH═CH₂ H —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉ 158-160I-2-b-6 CH₃ CH₃ CH═CH₂ H —(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉ 143-145 I-2-b-7CH₃ CH₃ CH═CH₂ H

t-C₄H₉ 155-157 I-2-b-8 CH₃ CH═CH₂ CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉145 I-2-b-9 CH₃ C₂H₅ CH₃ H —(CH₂)₅— t-C₄H₉ 96-98 I-2-b-10 CH₃ C₂H₅ CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉ 90-93 I-2-b-11 C₂H₅ C₂H₅ C₂H₅ H—(CH₂)₂—CHOCH₃—(CH₂)₂— H₅C₂—CHCH₃— Oil I-2-b-12 H CH₃ CH═CH₂ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— s-C₄H₉ Oil I-2-b-13 H CH═CH₂ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ Oil

Example III-1

At 80° C., 8.9 g of 2-ethyl-4-methyl-phenylacetic acid in 50 ml of drytoluene and 7.3 ml of thionyl chloride are stirred until evolution ofgas has ceased. Excess thionyl chloride is distilled off and the residueis taken up in 30 ml of dry toluene. At 0-10° C., this solution is addeddropwise to 8.6 g of ethyl 1-hydroxy-cyclohexanecarboxylate in 50 ml ofdry toluene, and the mixture is stirred at reflux for 8 h. The solutionis then concentrated using a rotary evaporator.

Yield: 16.6 g (

99% of theory)

The residue is used without further purification for the condensation togive Example I-2-a-1.

Example I-4-a-1

2.4 g of 2-ethyl-4,6-dimethyl-2-phenyl chlorocarbonyl ketene areinitially charged in ml of abs. xylene, and 1.5 g of4-fluoropropiophenone in 20 ml of abs. xylene are added dropwise. Themixture is heated at reflux for 8 hours. The xylene solution is washedwith water, dried over sodium sulphate and concentrated under reducedpressure. Chromatographic purification was carried out on silica gelusing the mobile phase toluene/ethanol 20:1.

Yield: 1 g (

28% of theory), of m.p. 161-162° C.

Example I-6-a-1

5.3 g of the compound of Example VIII-1 are initially charged in 50 mlof dry DMF and mixed with 2.95 g of potassium tert-butoxide, and themixture is heated at 60° C. for 1 h.

The reaction solution is admixed with 100 ml of 1 N HCl and extractedwith CH₂Cl₂, and the organic phase is dried and concentrated. Theresidue is purified by column chromatography (cyclohexane:ethyl acetate,5:1).

Yield: 2.35 g (49% of theory, m.p. 148° C.

1 g of the compound of Example I-6-a-1 is initially charged in 20 ml ofdry methylene chloride and admixed with 0.77 ml of triethylamine. 0.68ml of pivaloyl chloride is dissolved in 1 ml of methylene chloride andadded dropwise with ice-cooling, and the mixture is stirred at roomtemperature for 2 h.

The reaction solution is extracted twice with 10% citric acid solutionand the organic phase is washed twice with 1 N NaOH, dried andconcentrated.

Yield: 1.2 g (92% of theory) oil.

¹H-NMR (500 MHz, CDCl₃): δ=1.1 (s, 9H, —C(CH₃), 2.31 (s, 3H, Ar—CH₃);2.45 (q, 2H, Ar—CH ₂—CH₃) ppm

Example VIII-1

22.8 g of crude product from Example XXXIV-1 are initially charged in200 ml of dry acetone and admixed with 10.9 g of potassium carbonate,and 33.6 g (14.75 ml) of methyl iodide are added dropwise. The mixtureis stirred at reflux for 16 h.

The solvent is distilled off and the residue is purified by columnchromatography (methylene chloride/petroleum ether: 8:1).

Yield: 3.5 g (30% of theory), oil The product is used directly for thecyclization to give Example I-6-a-1.

Example XXXIV-1

11.2 g of monomethyl cyclohexanedicarboxylate, 5.3 ml of thionylchloride and a drop of DMF in 50 ml of dry toluene are heated at 100° C.until evolution of gas has ceased. The solvent is concentrated.

A solution of 50 ml LDA solution in 100 ml of dry THF is, at −15° C.,admixed dropwise with a solution of 17.3 g of methyl2-ethyl-4-methyl-phenylacetate in 20 ml of dry THF, and the mixture isstirred at this temperature for 30 min.

At −15° C., a solution of the freshly prepared acid chloride describedabove in 15 ml of dry THF is then added dropwise.

The mixture is stirred at room temperature for 1 hour, and 150 ml ofwater and 40 g of ammonium chloride are then added. The intermediate isextracted with ether and the solution is concentrated. The residue isboiled at reflux with 100 g of KOH and 330 ml of water for two days.

Yield: 23.70 g (91% of theory), oil

Example XXV-1

At room temperature, 4.7 g of lithium hydroxide, dissolved in 120 ml ofwater, are added dropwise to 26 g of the compound of Example XXX-1 in120 ml THF, and the mixture is stirred at room temperature for 8 h.

The reaction solution is concentrated using a rotary evaporator, admixedwith water and extracted with methyl tert-butyl ether.

The aqueous phase is adjusted to pH 2 using concentrated hydrochloricacid and the precipitate is filtered off with suction and dried.

Yield: 14 g (59% of theory), m.p.: 156.3° C.

Example XXX-1

At room temperature and under an atmosphere of argon, 0.27 g ofcopper(I) iodide, 0.745 g of triphenylphosphine and 1 g ofbis(triphenylphosphine)palladium dichloride are added with stirring to asolution of 7.32 g of methyl 2,6-dimethyl-4-bromo-phenylacetate(according to Example XXVI-1 from WO 97/02243) in 70 ml oftriethylamine, and 19.7 ml of trimethylsilyl-acetylene are then addeddropwise.

The reaction is monitored by gas chromatography.

Purification is carried out by silica gel column chromatography usingthe mobile phase petroleum ether/ethyl acetate, 20:1.

Yield: 6 g (73% of theory)

Example XXII-1

39 g of the compound of Example XXV-2 in 300 ml of thionyl chloride arestirred at 50° C. until evolution of gas has ceased.

Excess thionyl chloride is distilled off and the residue is taken up in30 ml of dry toluene and distilled.

Yield: 37 g (87% of theory), b.p.: 90-92° C. (0.05 mbar)

Example XXV-2

50 g of the compound of Example XXX-2 are admixed with 60 ml of ethanol,30 ml of water and 25 g of potassium hydroxide, and the mixture isheated at reflux for hours.

After the reaction has ended, the solvent is distilled off, the residueis dissolved in water and the mixture is acidified with conc.hydrochloric acid. The precipitate is filtered off with suction, washedand dried.

Yield: 41 g (93% of theory)

Example XXX-2 Process (P)

60 g of the compound of Ex. XLfI-1 are dissolved in 600 ml of ethanoland admixed with 50 ml of concentrated hydrochloric acid, and 5 g of 10%Pd/C are added.

At 120° C., a hydrogen pressure of 150 bar is applied to the reactionmixture.

After the reaction has ended, the mixture is filtered, the solvent isdistilled off and the residue is dissolved in 300 ml of methylenechloride, washed with 300 ml of water, dried and concentrated.

Yield: 51 g (91% of theory)

Example XLII-1

200 g of carbon disulphide and 86.7 g of aluminium chloride areinitially charged. At 0° C., 50 g of methyl 2-methylphenylacetate and28.2 g of propionyl chloride are added. The solution is stirred atreflux for 4 hours.

The solution is then poured onto 1 kg of ice-water and extracted with500 ml of methylene chloride.

The organic phase is washed with 10% strength hydrochloric acid and thenwith sodium carbonate solution, dried and concentrated.

Yield: 60 g (91% of theory)

Example XXV-3

30 g of the compound of Example XXX-3 in 32 ml of methanol and 16 ml ofwater are admixed with 12.2 g of potassium hydroxide, and the mixture isstirred at reflux for 5 h.

The solution is concentrated and the residue is taken up in water, themixture is washed with ethyl acetate and the aqueous phase is adjustedto pH 1 using cone. HCl.

The precipitate is filtered off with suction, washed and dried.

Yield: 25 g (99% of theory), m.p. 55-56° C.

Example XXX-3

20.8 g of the compound methyl 2,6-diethyl-4-bromo-phenylacetate(according to Example XXVI-6 from WO 97/02243) are dissolved in 100 mlof methanol. 7.2 g of sodium acetate and 2 g of palladium hydroxide areadded. The compound is then hydrogenated under pressure using hydrogen.

After the reaction has ended, the solution is filtered and concentrated.The residue is taken up in methylene chloride, washed with water, driedand concentrated.

Yield: 12 g (77% of theory)

USE EXAMPLES Example A Myzus Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested by thepeach aphids (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed.

In this test, the compounds of Preparation Examples I-2-a-4, I-2-b-5,I-2-b-6, I-1-a-6, I-1-c-4, I-4-a-1 exhibit, at an exemplary activecompound concentration of 1000 ppm, a kill of 100% after 6 days.

Example B Nephotettix Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of active compound of the desired concentrated and arepopulated with the green rice leaf hopper (Nephotettix cincticeps) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all leaf hoppers have been killed; 0% means that none of theleaf hoppers have been killed.

In this test, the compounds of Preparation Examples I-2-b-9, I-2-a-4,I-1-a-9, I-1-a-8, I-1-a-2. I-1-a-1, I-1-a-3, I-4-a-1, exhibit, at anexemplary active compound concentration of 1000 ppm, a kill of 100%after 6 days.

Example C Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, the compounds of Preparation Examples I-2-a-3, I-2-b-8,I-2-b-6, I-1-a-2, I-1-a-3, I-1-a-21, I-4-a-1 exhibit, at an exemplaryactive compound concentration of 1000 ppm, a kill of 100% after 7 days.

Example D Plutella Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the owlet moth (Plutella xylostella)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed: 0% means that none of thecaterpillars have been killed.

In this test, the compounds of Preparation Examples I-1-a-8, I-4-a-1exhibit, at an exemplary active compound concentration of 1000 ppm, akill of 100% after 7 days.

Example E Spodoptera Frugiperda Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the army worm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, the compound of Preparation Example I-2-a-3 exhibits, atan exemplary active compound concentration of 1000 ppm, a kill of 100%after 7 days.

Example F Tetranychus Test (OP-Resistant/Dip Treatment)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite (Tetranychus urticae) aredipped into a preparation of active compound of the desiredconcentration.

After the desired period of time, the effect in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites have been killed.

In this test, the compounds of Preparation Examples I-2-a-4, I-2-b-10,I-2-b-11, I-2-b-8, I-2-b-2, I-1-a-3, I-1-a-21, I-1-c-4, I-4-a-1 exhibit,at an exemplary active compound concentration of 1000 ppm, a kill of100% after 7 days.

Example G Bemisia Test

Solvent: 7.5 parts by weight of dimethylformamide

Emulsifier: 2.5 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentrations.

Cotton plants (Gossypium hirsutum) which are infested by eggs, larvaeand pupae of the white fly Bemisia tabaci are dipped into a preparationof active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals have been killed.

In this test, the compounds of Preparation Examples I-2-b-9, I-2-a-4,I-2-b-10 exhibit, at an exemplary active compound concentration of 1000ppm, a kill of 100% after 10 days.

Example H Post-Emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: I part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants of a height of 5-15 cm are sprayed with the preparation ofactive compound such that the particular amounts of active compounddesired are applied per unit area. The concentration of the spray liquoris chosen such that the particular amount of active compound desired isapplied in 1000 l of water/ha.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control.

The figures denote:

-   -   0%=no effect (like untreated control)    -   100%=total destruction

Example I Pre-Emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkyaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours,the soil is sprayed with the preparation of active compound such thatthe particular amounts of active compound desired are applied per unitarea. The concentration of the spray liquor is chosen such that theparticular amounts of active compound desired are applied in 1000 l ofwater/ha.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated controls.

The figures denote:

-   -   0%=no effect (like untreated control)    -   100%=total destruction

Post-emergence g ai/ha Wheat Cotton Alopecurus Avena fatua LoliumSorghum Ex. I-2-a-4 60 0 0 95 80 95 80 Post- emergence g ai/ha Sugarbeet Alopecurus Avena fatua Digitaria Lolium Setaria Ipomoea PolygonumEx. I-1-a-21 125 0 100 90 100 95 99 70 — Ex. I-1-c-4 60 10 90 90 95 —100 — 70 Post-emergence g ai/ha Soya bean Digitaria Lolium SetariaSorghum Galium Ex. I-1-a-5 125 10 90 — 100 95 80 Ex. I-1-a-3 125 — 80 7090 — 80 Oilseed Post-emergence g ai/ha Sugar beet rape Digitaria LoliumSetaria Sorghum Galium Ex. I-I-a-2 125 0 0 80 70 95 80 80 Post-emergenceg ai/ha Sugar beet Cotton Alopecurus Avena fatua Digitaria Setaria Ex.I-1-a-9 15 10 0 100 95 95 100 Post-emergence g ai/ha Sugar beet CottonDigitaria Echinochloa Setaria Sorghum Ex. I-1-a-8 60 10 0 95 100 100 95Post-emergence g ai/ha Digitaria Lolium Setaria Sorghum Ex. I-1-a-6 12595 80 95 100 Post-emergence g ai/ha Wheat Soya bean Cotton DigitariaLolium Setaria Ex. I-2-b-12 125 — 0 0 95 90 95 Ex. I-2-b-13 125 10 0 080 70 95 Post-emergence g ai/ha Wheat Sugar beet Cotton DigitariaEchinochloa Setaria Sorghum Ex. I-4-a-1 125 20 0 0 100 90 95 90Post-emergence g ai/ha Wheat Lolium Cassia Solanum Viola Ex. I-2-b-10125 10 80 95 80 90 Soya Pre-emergence g ai/ha Wheat Maize Sugar beetbean Alopecurus Avena fatua Bromus Lolium Setaria Ex. I-2-a-4 125 — 5 00 100 80 70 100 100 Ex. I-1-a-8 60 0 10 0 0 100 90 100 100 100Pre-emergence g ai/ha Alopecurus Avena fatua Digitaria EchinochloaLolium Setaria Ex. I-1-a-3 125 100 95 100 100 100 100 Pre-emergence gai/ha Alopecurus Avena fatua Echinochloa Ex. I-1-a-6 60 90 80 90Pre-emergence g ai/ha Sugar beet Soya bean Alopecurus Digitaria LoliumSetaria Veronica Ex. I-4-a-1 125 0 0 100 100 100 100 95 Ex. I-1-a-21 1250 0 100 100 100 100 100 Ex. I-1-a-9 125 0 0 100 100 100 100 90Pre-emergence g ai/ha Wheat Soya bean Alopecurus Echinochloa LoliumSetaria Chenopodium Ex. I-1-a-5 60 0 0 100 100 100 100 70 SoyaPre-emergence g ai/ha bean Alopecurus Bromus Cyperus Digitaria LoliumSetaria Abutilo Ex. I-1-c-4 125 20 95 100 100 100 100 100 70

Example J Critical Concentration Test/Soil Insects—Treatment ofTransgenic Plants

Test insects: Diabrotica balteata—larvae in soil

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, I part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil. Here, theconcentration of the active compound in the preparation is almostirrelevant, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.25 l pots and these are allowed to stand at 20° C.

Immediately after preparation, 5 pre-germinated maize corns of thevariety YIELD GUARD (trade mark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the test insects are placed into the treatedsoil. After a further 7 days, the efficacy of the active compound isdetermined by counting the maize plants that have emerged (1 plant=20%efficacy).

Example K Heliothis Virescens Test—Treatment of Transgenic Plants

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (glycine max) of the variety Roundup Ready (trade markof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and are populated withthe tobacco budworm Heliothis virescens while the leaves are stillmoist.

After the desired period of time, the kill of the insects is determined.

What is claimed is:
 1. A compound of the formula (I-6-A) and/or (I-6-B)

in which W represents methyl, X represents C₁-C₆-alkyl, C₂-C₆-alkenyl orethinyl, Y represents hydrogen, methyl, ethyl, i-propyl, C₂-C₆-alkenylor ethinyl, Z represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl orethinyl, with the proviso that at least one of the radicals X, Y or Zrepresents a chain having at least two carbon atoms and with the furtherproviso that X is not ethyl when Z is hydrogen and Y is methyl, Brepresents hydrogen, A and Q¹ together represent C₄-alkanediyl, Q²represents hydrogen, and G represents hydrogen (a) or

in which R¹ represents C₁-C₆-alkyl, C₂-C₆-alkenyl,C₁-C₂-alkoxy-C₁-alkyl, C₁-C₂-alkylthio-C₁-alkyl or cyclohexyl orcyclopropyl which is optionally monosubstituted by fluorine, chlorine,methyl or methoxy, or represents phenyl which is optionallymonosubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl,methoxy, trifluoromethyl or trifluoromethoxy.
 2. A process for preparinga compound of the formula (I), wherein (A) a compound of the formula(I-6-a)

in which A, B, Q¹, Q², W, X, Y and Z are each as defined in claim 1, isobtained by intramolecular cyclization of a ketocarboxylic ester of theformula (VIII)

in which A, B, Q¹, Q², W, X, Y and Z are each as defined in claim 1, andR⁸ represents alkyl, if appropriate in the presence of a diluent and ifappropriate in the presence of a base; or (B) a compound of the formula(I-6-a) or (I-6-b)

in which A, B, D, G, Q¹, Q², W, X, Y and Z are each as defined in claim1, where one or at most two radicals X, Y or Z represent R²²—C≡C— or

 and R²² represents hydrogen, is obtained by reacting a compound of theformula (I-6′(a-g))

in which A, B, D, G, Q¹, W′, X′, Y′ and Z′ are each as defined in claim1, and Q² is as defined above, and where the apostrophe ' means that oneor at most two radicals X, Y and Z in this process represent chlorine,bromine or iodine, with the proviso that the other radicals X, Y and Zdo not represent alkenyl or alkinyl with a silylacetylene of the formula(X-a) or a vinylstannane of the formula (X-b)

in which Alk represents C₁-C₄-alkyl, R²¹ represents C₁-C₄-alkyl orphenyl, and R²² represents hydrogen, in the presence of a solvent, ifappropriate in the presence of a base and a catalyst; or (C) a compoundof the formula (I-6-b) shown above in which A, B, D, Q¹, Q², R¹, W, X, Yand Z are each as defined in claim 1 is obtained by reacting a compoundof the formula (I-6-a) shown above in which A, B, D, Q¹, Q², W, X, Y andZ are each as defined in claim 1, (α) with an acid halide of the formula(XI)

in which R¹ is as defined in claim 1 and Hal represents halogen or (β)with a carboxylic anhydride of the formula (XII)R¹—CO—O—CO—R¹  (XII) in which R¹ is as defined in claim 1, ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid binder.
 3. A compound of the formula (I) accordingto claim 1, wherein W represents methyl, X represents C₁-C₄-alkyl,C₂-C₄-alkenyl or ethinyl, Y represents hydrogen, methyl, ethyl,i-propyl, C₂-C₄-alkenyl or ethinyl, Z represents hydrogen, C₁-C₄-alkyl,C₂-C₄-alkenyl or ethinyl, with the proviso that at least one of theradicals X, Y or Z represents a chain having at least two carbon atoms,where at most only one of the radicals X, Y or Z may representC₂-C₄-alkenyl or ethinyl, and with the further proviso that X is notethyl when Z is hydrogen and Y is methyl, B represents hydrogen orC₁-C₄-alkyl, A and Q¹ together represent C₄-alkanediyl, Q² representshydrogen, and G represents hydrogen (a)

in which R¹ represents C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₂-alkoxy-C₁-alkyl, C₁-C₂-alkylthio-C₁-alkyl or cyclohexyl orcyclopropyl which is optionally monosubstituted by fluorine, chlorine,methyl or methoxy, or represents phenyl which is optionallymonosubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl,methoxy, trifluoromethyl or trifluoromethoxy.
 4. A compound of theformula (I) according to claim 1, wherein W represents methyl, Xrepresents methyl, ethyl, n-propyl, iso-propyl, vinyl or ethinyl, Yrepresents hydrogen, methyl, ethyl, i-propyl, vinyl or ethinyl, Zrepresents hydrogen, methyl, ethyl, n-propyl, i-butyl, vinyl or ethinyl,with the proviso that at least one of the radicals X, Y or Z representsa chain having at least two carbon atoms, where at most only one of theradicals X, Y or Z may represent vinyl or ethinyl, and with the furtherproviso that X is not ethyl when Z is hydrogen and Y is methyl, Brepresents hydrogen, methyl or ethyl, A and Q¹ together representC₄-alkanediyl, Q² represents hydrogen, and G represents hydrogen (a) or

in which R¹ represents C₁-C₆-alkyl, C₂-C₆-alkenyl,C₁-C₂-alkoxy-C₁-alkyl, C₁-C₂-alkylthio-C₁-alkyl or cyclohexyl orcyclopropyl which is optionally monosubstituted by fluorine, chlorine,methyl or methoxy, represents phenyl which is optionally monosubstitutedby fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy,trifluoromethyl or trifluoromethoxy.
 5. A pesticide or herbicide thatcomprises at least one compound of the formula (I) according to claim 1.6. A method for controlling animal pests comprising allowing a compoundof the formula (I) according to claim 1 to act on pests and/or theirhabitat.
 7. A method of controlling undesirable vegetation comprisingusing a compound of formula (I) according to claim
 1. 8. A process forpreparing a pesticides or herbicide comprising mixing a compound of theformula (I) according to claim 1 with extenders and/or surfactants.